NO162244B - SILICONE-CONTAINING POLYMERS WITH HIGH OXYGEN PERMEABILITY AND PROCEDURES FOR PREPARING IT. - Google Patents
SILICONE-CONTAINING POLYMERS WITH HIGH OXYGEN PERMEABILITY AND PROCEDURES FOR PREPARING IT. Download PDFInfo
- Publication number
- NO162244B NO162244B NO833700A NO833700A NO162244B NO 162244 B NO162244 B NO 162244B NO 833700 A NO833700 A NO 833700A NO 833700 A NO833700 A NO 833700A NO 162244 B NO162244 B NO 162244B
- Authority
- NO
- Norway
- Prior art keywords
- methacrylate
- monomer
- water
- monomers
- formula
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 35
- 239000001301 oxygen Substances 0.000 title claims description 35
- 229910052760 oxygen Inorganic materials 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 24
- 230000035699 permeability Effects 0.000 title description 24
- -1 polysiloxane Polymers 0.000 claims abstract description 163
- 239000000178 monomer Substances 0.000 claims abstract description 129
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims description 20
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 16
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 8
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 claims description 7
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003926 acrylamides Chemical class 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 6
- FMQPBWHSNCRVQJ-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F FMQPBWHSNCRVQJ-UHFFFAOYSA-N 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005227 gel permeation chromatography Methods 0.000 claims description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940114077 acrylic acid Drugs 0.000 claims 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- 229940063559 methacrylic acid Drugs 0.000 claims 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- 150000001408 amides Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006037 cross link polymer Polymers 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229940048053 acrylate Drugs 0.000 description 8
- 210000004087 cornea Anatomy 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 239000004945 silicone rubber Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 210000001508 eye Anatomy 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000004662 dithiols Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 201000009310 astigmatism Diseases 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- VVYDVQWJZWRVPE-UHFFFAOYSA-L dimethyltin(2+);diiodide Chemical compound C[Sn](C)(I)I VVYDVQWJZWRVPE-UHFFFAOYSA-L 0.000 description 1
- 125000001303 disiloxanyl group Chemical group [H][Si]([*])([H])O[Si]([H])([H])[H] 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- NVLHKSGUMYMKRR-UHFFFAOYSA-N dodeca-2,10-dienediamide Chemical compound NC(=O)C=CCCCCCCC=CC(N)=O NVLHKSGUMYMKRR-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 231100000040 eye damage Toxicity 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- OXZMJPQKHGOTGJ-UHFFFAOYSA-N n-[10-(prop-2-enoylamino)decyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCCCCCNC(=O)C=C OXZMJPQKHGOTGJ-UHFFFAOYSA-N 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- ZBUXMZFLCYRTOB-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C.CNC(=O)C=C ZBUXMZFLCYRTOB-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- FEZFGASTIQVZSC-UHFFFAOYSA-N nonanoyl nonaneperoxoate Chemical compound CCCCCCCCC(=O)OOC(=O)CCCCCCCC FEZFGASTIQVZSC-UHFFFAOYSA-N 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- 229920005787 opaque polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 231100000330 serious eye damage Toxicity 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QHDZGOLELSOUFO-UHFFFAOYSA-N tert-butyl butaneperoxoate Chemical compound CCCC(=O)OOC(C)(C)C QHDZGOLELSOUFO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical group CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/148—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Eyeglasses (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Road Signs Or Road Markings (AREA)
- Confectionery (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
Oppfinnelsen vedrører klare, sterke, kryssbundne polymerer som fåes ved kopolymerisasjon av (A) en rettkjedet eller forgrenet polysiloksan-makromer inneholdende i det minste 2 endestående eller vedhengende (eng.: pendant), polymeriserbare vinylgrupper bundet til polysiloksanet ved hjelp av en uretan-, tiouretan-, urea-eller amidgruppe, og (B) et vinyl eller divinylmonomer eller blandinger av monomerer, hvilke monomerer består av 85-100% vann-uoppløselige monomerer, hvilke polymerer er egnet ved fremstilling av myke eller hårde kontaktlinser, spesielt de hårde linser. The invention relates to clear, strong, cross-linked polymers which are obtained by copolymerization of (A) a straight-chain or branched polysiloxane macromer containing at least 2 terminal or pendant polymerizable vinyl groups bound to the polysiloxane by means of a urethane, thiourethan, urea or amide group, and (B) a vinyl or divinyl monomer or mixtures of monomers, which monomers consist of 85-100% water-insoluble monomers, which polymers are suitable in the manufacture of soft or hard contact lenses, especially the hard lenses .
Kontaktlinser oppdeles i to hovedkategorier, vanligvis kalt "hårde" og "myke", men som bedre adskiller seg ved hvilken måte de er tilpasset øyet. Hårde kontaktlinser er heller løst tilpasset for å bevirke utbytte av tårevæske mellom linser og hornhinne, hvilken bevirkes ved deres "jyngestol"-bevegelse, ved hvilken de kontinuerlig pumper tårevæske ut fra rommet mellom linsen og øyets overflate. Slikt tårevæskeutbytte er den eneste måte ved hvilken all viktig oksygen tilføres hornhinnen til bæreren av konvensjonelle hårde kontaktlinser fremstilt av polymetylmetakrylat (PMMA). Contact lenses are divided into two main categories, usually called "hard" and "soft", but which are better distinguished by the way they are adapted to the eye. Rather, hard contact lenses are loosely adapted to effect exchange of tear fluid between the lens and cornea, which is accomplished by their "highchair" motion, whereby they continuously pump tear fluid out of the space between the lens and the surface of the eye. Such tear fluid yield is the only means by which all important oxygen is supplied to the cornea of the wearer of conventional hard contact lenses made of polymethyl methacrylate (PMMA).
Skjønt hårde PMMA linser er, i det minste i begynnelsen, ubekvemme og irriterende for bæreren på grunn av at det blink-ende øyelodd treffer en hård kant, er de ikke desto mindre populære på grunn av at de kan fremstilles med stor presisjon ved dreiing og polering. Dette er spesielt viktig for korreksjon av astigmatisme med linser av asymmetrisk utførelse. En annen fordel er at de er meget lett å holde rene, hvorved det trenges ingen sterilisering. Although hard PMMA lenses are, at least initially, uncomfortable and irritating to the wearer due to the blinking eyeball hitting a hard edge, they are nevertheless popular because they can be manufactured with great precision by turning and polishing. This is particularly important for the correction of astigmatism with lenses of asymmetrical design. Another advantage is that they are very easy to keep clean, whereby no sterilization is needed.
Myke kontaktlinser fester seg på den andre side tett til hornhinnen og er derfor mye mer behagelig for bæreren, da de kun tillater begrenset tårevæskeutbytte, må de ha en tilstrekkelig høy oksygenpermeabilitet for å forhindre øye-skade endog om de er blitt båret kun for noen få timer. Soft contact lenses, on the other hand, adhere closely to the cornea and are therefore much more comfortable for the wearer, as they only allow limited tear fluid yield, they must have a sufficiently high oxygen permeability to prevent eye damage even if they have been worn for only a few hours.
I alle kommersielle myke kontaktlinser er denne C^-permea-blilitet en funksjon av deres vanninnehold, som er en egen-skap med hydrogeler. Dessuten virker vann som et myknings- middel, som gir linsen dets mykhet og de nødvendige hydro-filiske egenskaper som muliggjør den å svæmme og rotere på hornhinnen, heller enn å klebe seg til denne. Klebing til hornhinnen er hovedproblemet med hydrogfobe, myke linser, slik som de ellers meget tiltrekkende silikon-gummi-linser. Skjønt hydrogel-myke linser representerer fremskritt ved komfort, gjøres det kompromisser med hensyn til presisjon, da noen forvrengninger på grunn av vannsvelling er uunngåe-lige, da de er tilbøyelig til å rotere på øyet og i tillegg er astigmatisme et mye vanskeligere problem å løse. Dessuten er proteinadsorbsjon og desinfeksjon hovedproblemene og økning i komfort blir i stor ustrekning balansert med større besvær ved mer innviklede prosedyrer ved linserenhold. In all commercial soft contact lenses, this C₂ permeability is a function of their water content, which is a property of hydrogels. In addition, water acts as a softening agent, giving the lens its softness and the necessary hydrophilic properties that enable it to float and rotate on the cornea, rather than sticking to it. Adhesion to the cornea is the main problem with hydrophobic, soft lenses, such as the otherwise very attractive silicone-rubber lenses. Although hydrogel soft lenses represent advances in comfort, compromises are made in terms of precision, as some distortion due to water swelling is inevitable, as they are prone to rotating on the eye and, in addition, astigmatism is a much more difficult problem to solve . Moreover, protein adsorption and disinfection are the main problems and the increase in comfort is largely balanced by greater difficulty in more complicated procedures for lens cleaning.
Den neste viktige utviklingen i kontaktlinse-teknologi var fremstillingen av linser som kunne bæres kontinuerlig, dag og natt, for opptil flere uker. Oksygenpermeabilitet av linsene må økes mange ganger for dette formål på grunn av at ved lukket øye-stilling under søvn, forsynes hornhinnene med all oksygen fra det blod-overførende øyelokk. Blant de forskjellige problemløsninger som ikke har lykkes tilfreds-stillende med hensyn til dette, er: (-]) hydrogeler med høyt vanninnhold opp til 70% vann, deres ulempe er mekanisk svakhet og på grunn av dette må de fremstilles tykkere og (^-permeabilitet blir derfor minsket, og (B) silikongummilinser som fullstendig har mislykkes på grunn av deres ekstreme vannav-støtende egenskaper, de fester seg lik en sugekopp til hornhinnen og leder til alvorlige øyeskader. Forsøk på å gjøre overflaten til silikongummilinsene tilstrekkelig hydrofil for å forhindre dette, har ikke blitt altfor vellykket, mest på grunn av at det behandlede overflateområdet er for tynt for å være permanent. F..eks. er de linser som er fremstillet av DOW CORNING under handelsnavnet "SILICON" og "SILSOFT" behandlet for å danne et -Si-OH overflatesjikt som imidlertid er så tynt at det lett slites av, spesielt på en hård linse. Det er et formål ved oppfinnelsen å fremskaffe en silikoninneholdende,. hård linse hvis overflate er permanent fuktbar. En annen ulempe med 100% silikongummi kontaktlinser er vanskeligheten med hvilke kantene kan slutt-behandles og poleres, og dermed gjøres bekvemme for bæreren, . dette er et iboende problem med alle gummiaktige mateialer. Det er et ytterligere formål ved oppfinnelsen å fremskaffe silikoninneholdende polymermaterialet som varierer fra "myk" til "hård" - ifølge kontaktlinse-terminologien - men som alle er lett polerbare. The next important development in contact lens technology was the production of lenses that could be worn continuously, day and night, for up to several weeks. Oxygen permeability of the lenses must be increased many times for this purpose, because in the closed eye position during sleep, the corneas are supplied with all the oxygen from the blood-transmitting eyelid. Among the various problem solutions that have not succeeded satisfactorily in this respect are: (-]) hydrogels with a high water content of up to 70% water, their disadvantage is mechanical weakness and because of this they must be produced thicker and (^- permeability is therefore reduced, and (B) silicone rubber lenses which have completely failed due to their extreme water repellency, stick like a suction cup to the cornea and lead to serious eye damage Attempts to make the surface of the silicone rubber lenses sufficiently hydrophilic to prevent this, has not been too successful, mostly because the treated surface area is too thin to be permanent, eg the lenses manufactured by DOW CORNING under the trade names "SILICON" and "SILSOFT" are treated to form a -Si-OH surface layer which, however, is so thin that it easily wears off, especially on a hard lens. It is an object of the invention to provide a silicone-containing, hard lens if ove rflate is permanently wettable. Another disadvantage of 100% silicone rubber contact lenses is the difficulty with which the edges can be finished and polished, and thus made comfortable for the wearer. this is an inherent problem with all rubbery materials. It is a further object of the invention to provide the silicone-containing polymer material which varies from "soft" to "hard" - according to contact lens terminology - but all of which are easily polishable.
Eksempler av nyere dato på silikoninneholdende hydrofobe polymerer er beskrevet US-PS 4.153.641, 4.189.546 og 4.195.030 og de består av polymerisert eller kopolymerisert polysiloksan eller polyparafin-siloksan-diakrylater og metakrylater med høy molekylvekt. De resulterende polymerer er hydrofobe. US-PS 4.217.038 beskriver en overflatebehand-ling for oppnåelse av hydrofile overflater. Andre kontakt-linsematerialer som inneholder polysiloksaner, er beskrevet i US-PS nr. 4.208.362, 4.208.506, 4.254.248, 4.259.467, 4.277.595, 4.260.725 og 4.276.402. Alle disse patenter baseres på bis-metakrylat estrer av rettkjedede polysiloksandioler. På grunn av den myke natur av rettkjedede polysiloksaner, er de ikke egnet for å fremstille hårde, stive materialer som er nødvendig for en hård kontaktlinse. US- Recent examples of silicone-containing hydrophobic polymers are described in US-PS 4,153,641, 4,189,546 and 4,195,030 and they consist of polymerized or copolymerized polysiloxane or polyparaffin-siloxane diacrylates and high molecular weight methacrylates. The resulting polymers are hydrophobic. US-PS 4,217,038 describes a surface treatment for obtaining hydrophilic surfaces. Other contact lens materials containing polysiloxanes are described in US-PS Nos. 4,208,362, 4,208,506, 4,254,248, 4,259,467, 4,277,595, 4,260,725 and 4,276,402. All these patents are based on bis-methacrylate esters of straight-chain polysiloxanediols. Because of the soft nature of straight-chain polysiloxanes, they are not suitable for making the hard, rigid materials necessary for a hard contact lens. US
PS nr. 4.136.250 beskriver i tillegg til de ovenfor nevnte bis-metakrylater av rettkjedede polysiloksan-dioler også bis- og tris-metakrylater av dioler og trioler i hvilke de funksjonelle grupper er vedhengende, ikke endestående, PS No. 4,136,250 describes, in addition to the above-mentioned bis-methacrylates of straight-chain polysiloxane diols, also bis- and tris-methacrylates of diols and triols in which the functional groups are pendant, not terminal,
til hovedpolysiloksankjeden, og dessuten forbindelser som er forbundet til polysiloksanet med bis-urean-bindinger. Alle sammensetninger er imidlertid hydrogeler og som sådanne er de kun egnet for myke kontaktlinser. to the main polysiloxane chain, and also compounds which are connected to the polysiloxane by bis-ureane linkages. However, all compositions are hydrogels and as such are only suitable for soft contact lenses.
En stiv silikon-inneholdende hård linse er beskrevet i US-PS r. 4.152.508 og den består av en kopolymer av et oligo-siloksanyl-alkyl-akrylat med forskjellige komonomerer, slik som dimetyl-itakonat og metylmetakrylat. Skjønt det påstås A rigid silicone-containing hard lens is described in US-PS r. 4,152,508 and it consists of a copolymer of an oligo-siloxanyl-alkyl acrylate with various comonomers, such as dimethyl itaconate and methyl methacrylate. Although it is claimed
«.,,.- ,n-10 cm3(STP).cm . , permeabiliteter pa 3-50x10 -H—; =— gjør de høye mengder av oligosiloksan-substituert metakrylat (>40%) som «.,,.- ,n-10 cm3(STP).cm . , permeabilities of 3-50x10 -H—; =— do the high amounts of oligosiloxane-substituted methacrylate (>40%) which
ei nødvendig for å få G^-permeabiliteter høyere enn 9, polymeren samtidig for myk for å være egnet som en hård linse. Kun dersom Si-monomer bestanddelene er mindre enn 25% av polymeren, er polymer-hårdheten tilstrekkelig høy for hård kontaktlinse-anvendelse. Da siloksan-innholdet også innvirker ugunstig på fukteevnen, er det- naturligvis en fordel å anvende så lite Si i polymeren som mulig, akku-rat tilstrekkelig for å få den nødvendige G^-permeabilitet. not necessary to get G^ permeabilities higher than 9, the polymer at the same time too soft to be suitable as a hard lens. Only if the Si monomer components are less than 25% of the polymer, the polymer hardness is sufficiently high for hard contact lens use. As the siloxane content also has an adverse effect on the wetting ability, it is naturally an advantage to use as little Si in the polymer as possible, just enough to obtain the required G^ permeability.
Siloksanuretan-akrylat-forbindelser som er egnet for fremstilling av belegningssammensetninger for-stråleherding er beskrevet i US-PS nr. 4.130.708. Disse siloksanurean-akrylat-forbindelser kan blandes med andre ingredienser som vanligvis finnes i belegningssammensetninger og stråle-herdes med UV-lys. Anvendelsen av slike materialer for kontaktlinser er hverken beskrevet eller foreslått i dette patent. Belegningssammensetningene som er beskrevet i paten-tet, omfatter ikke noen hydrofile monomerkomponenter. Siloxanurethane acrylate compounds suitable for the preparation of coating compositions for radiation curing are described in US-PS No. 4,130,708. These siloxanurean acrylate compounds can be mixed with other ingredients commonly found in coating compositions and radiation cured with UV light. The use of such materials for contact lenses is neither described nor suggested in this patent. The coating compositions described in the patent do not include any hydrophilic monomer components.
GB-PS nr. 2.067.213 beskriver også siloksanuretan-akrylat-forbindelser som er egnet for fremstilling av fotoherdbare belegningssammensetninger. Anvendelsen av slike materialer for kontaktlinser er ikke beskrevet. Belegningssammensetningene som er beskrevet i dette patent, omfatter ikke noen hydrofile monomer-komponenter, heller ikke er de hydrofobe komonomerer beskrevet i denne oppfinnelse. GB-PS No. 2,067,213 also describes siloxanurethane acrylate compounds which are suitable for the production of photocurable coating compositions. The use of such materials for contact lenses is not described. The coating compositions described in this patent do not include any hydrophilic monomer components, nor are the hydrophobic comonomers described in this invention.
Us-patent nr. 4.341.889 omfatter kryssbundne polymere bestående av a) polysiloksaner med polymeriserbare endeplasserte grupper, US patent no. 4,341,889 covers cross-linked polymers consisting of a) polysiloxanes with polymerizable terminal groups,
b) tert.-butylstyren og c) hydrofile vinylmonomere. Derved betyr den bivalente gruppe R som i polysiloksanene a) forbinder b) tert-butylstyrene and c) hydrophilic vinyl monomers. Thereby means the bivalent group R which in the polysiloxanes a) connects
silisium og de polymeriserbare endeplasserte grupper alltid alkylen eller arylen. Anvendelse av diisocyanat omtales over hodet ikke, mens i foreliggende oppfinnelse er diisocyanat vesentlig. silicon and the polymerizable terminal groups always the alkylene or the arylene. The use of diisocyanate is not mentioned above, whereas in the present invention diisocyanate is essential.
Det er kjent at SiO(CH3)2er en mer virkningsfull oksygen-transmitter dersom den er tilstede i form av siloksanpolymer enn dersom den er kun en del av en lav-molekylvekt: side-gruppe. De lange polysiloksankjeder som er tilstede i sammensetninger ifølge US-PS nr. 4.153.641 og beslektede patenter reduserer imidlertid kraftig stivhet, og leder til gummiaktige og myke materialer. Dessuten er deres forenlighet ned slike ubeslektede polymerer som polymetakrylater dårligDg faseseparasjon, typisk for blandinger av høy molekylær vekt polymerer, leder til mer eller mindre opake produkter. It is known that SiO(CH3)2 is a more effective oxygen transmitter if it is present in the form of a siloxane polymer than if it is only part of a low molecular weight: side group. However, the long polysiloxane chains present in compositions of US-PS No. 4,153,641 and related patents greatly reduce stiffness, leading to rubbery and soft materials. Moreover, their compatibility with such unrelated polymers as polymethacrylates is poor due to phase separation, typical of mixtures of high molecular weight polymers, leading to more or less opaque products.
Det har nå blitt uventet oppdaget at dersom polyfunksjonelle hrtvmolekylære polysiloksaner hvis ekvivalent-vekt ikke er større enn f.eks. og som er bundet til i det minste to endestående eller vedhengende polymeriserbare vinylgrupper av bis-uretan-bindinger blandes i en kryssbundet vinylkopoly-mer, fås hårde, stive og klare produkter som har utmerket 02-permeabilitet, opp til 4 ganger høyere enn for den beste tidligere kjente sammensetning, og som endog ved et siloksan-innhold på >50% er tilstrekkelig stiv for å oppfylle kravene for en hård kontaktlinse. Det er videre, meget uventet, blitt funnet at siloksaninneholdende polymerer ifølge oppfinnelsen kan fremstilles med bedre fukteevne enn konvensjonelle PMMA hård linser, på tross av deres høye polysiloksan-innhold. It has now been unexpectedly discovered that if polyfunctional hrtvmolecular polysiloxanes whose equivalent weight is not greater than e.g. and which are bound to at least two terminal or pendant polymerizable vinyl groups of bis-urethane linkages are mixed in a cross-linked vinyl copolymer, hard, rigid and clear products are obtained which have excellent O2 permeability, up to 4 times higher than that of the best previously known composition, and which, even with a siloxane content of >50%, is sufficiently rigid to meet the requirements for a hard contact lens. It has further, very unexpectedly, been found that siloxane-containing polymers according to the invention can be produced with better wettability than conventional PMMA hard lenses, despite their high polysiloxane content.
De foretrukne polysiloksan makromerer for syntetse av hårde kontaktlinse-materialer er slike som inneholder (a) i det minste en uretan-bindingsgruppe pr. 12 fSiO(CH3)24enheter; (b) som inneholder i det misnte to polymeriserbare vinylgrupper bundet vedhengende til polysiloksan-hovedkjeden og derfor inneholder i det minste to endestående fSitCH^)-^ enheter; og (c) inneholder uretangrupper avledet fra voluminøse, :cykloalifatiske diisocyanater. De foretrukne komonomerer som kan inngå forbindelse med polysiloksan-makromerene, The preferred polysiloxane macromers for synthesizing hard contact lens materials are those which contain (a) at least one urethane linking group per 12 fSiO(CH3)24 units; (b) containing at least two polymerizable vinyl groups attached pendantly to the polysiloxane backbone and therefore containing at least two terminal fSitCH^)-^ units; and (c) contains urethane groups derived from bulky, cycloaliphatic diisocyanates. The preferred comonomers which can form a connection with the polysiloxane macromers,
er akrylater og metakrylater som når polymerisert med seg selv gir hårde homopolymerer med en høy glass-omvandlings- are acrylates and methacrylates which, when polymerized with themselves, give hard homopolymers with a high glass transition
temperatur, slik som metyl-metakrylat, isopropyl-, isobutyl-, tert.butyl-, cykloheksyl- eller isobornyl-metakrylat. temperature, such as methyl methacrylate, isopropyl, isobutyl, tert.butyl, cyclohexyl or isobornyl methacrylate.
Skjønt oppfinnelsen primært er rettet mot hårde kontakt-linsematerialer, er' det også funnet at klare, sterke, men gummiaktige polymerer kan fremstilles. Slike polymerer som er egnet for forskjellige formål som bioforenlige implantanter, bandasje for sårbehandling eller som myke kontaktlinser, er således et annet formål ved oppfinnelsen. Although the invention is primarily aimed at hard contact lens materials, it has also been found that clear, strong but rubbery polymers can be produced. Such polymers which are suitable for various purposes such as biocompatible implants, bandages for wound treatment or as soft contact lenses, are thus another purpose of the invention.
Det er således innen rammen av oppfinnelsen å anvende komonomerer som vil gi sterke, og fleksible og gummiaktige polymerer . It is thus within the scope of the invention to use comonomers which will give strong, flexible and rubbery polymers.
Oppfinnelsen vedrører polymer som egner seg for fremstilling av kontaktlinser og som erkarakterisert vedat den består av et kryssbundet polymerisasjonsprodukt av A) fra 15 til 60 vekt-% av en lineær eller forgrenet polysiloksanmakro-mer med en molekylvekt fra 400 til 1 00 000 , målt ved endegruppeanalyse eller gelgjennomtrengningskromatografi, The invention relates to polymer which is suitable for the production of contact lenses and which is characterized in that it consists of a cross-linked polymerization product of A) from 15 to 60% by weight of a linear or branched polysiloxane macromer with a molecular weight from 400 to 100,000, measured by end group analysis or gel permeation chromatography,
idet den makromere inneholder minst to endestående eller vedhengende (pendant) polymeriserbare olefiniske grupper pr. hver 5000 molekylvektenheter av polysiloksan, idet gruppene er forbundet til polysiloksanet med i det minst to uretan-, tiouretan-, urea- eller amidbindinger, idet makromeren har strukturen A1eller A„ in that the macromer contains at least two terminal or pendant polymerizable olefinic groups per each 5,000 molecular weight units of polysiloxane, the groups being connected to the polysiloxane with at least two urethane, thiourethane, urea or amide bonds, the macromer having the structure A1 or A„
hvori er en lineær eller forgrenet alkylengruppe med 2-6 karbonatomer eller en polyoksyalkylengruppe med struktur G in which is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structure G
hvori R3er hydrogen eller metyl, og n er et helt tall på 1-50,<R>2, Ra, Rb, Rc, Rd, Re. Rf. Rg»»h»Ri'Rj°SRkbetyr metyl, X^og X2er hele tall fra 1-500, med det forbehold at summen av X^pluss X2er 7 til 100, y^betyr 0 til 14 og Y2betyr 1 til 13, med det forbehold at forholdet av X} + X2eller X^+ X2ikke er større enn 70, wherein R3 is hydrogen or methyl, and n is an integer from 1-50,<R>2, Ra, Rb, Rc, Rd, Re. Rf. Rg»»h»Ri'Rj°SRkmeans methyl, X^and X2 are whole numbers from 1-500, with the proviso that the sum of X^plus X2 is 7 to 100, y^means 0 to 14 and Y2means 1 to 13, with provided that the ratio of X} + X2or X^+ X2 is not greater than 70,
Y1+ 2 Y2+ 1 Y1+ 2 Y2+ 1
X er et diradikalt med formel C X is a diradical of formula C
hvori Zi betyr oksygen, svovel eller NR5, og R5betyr hydrogen eller lavere (C1-C4) alkyl, Z^er forbundet med Rj; wherein Z 1 is oxygen, sulfur or NR 5 , and R 5 is hydrogen or lower (C 1 -C 4 ) alkyl, Z 2 is linked to R 1 ;
og R4er det divalente radikal dannet ved å fjerne NCO-grupper fra et alifatisk eller cykloalifatisk diisocyanat; and R 4 is the divalent radical formed by removing NCO groups from an aliphatic or cycloaliphatic diisocyanate;
Y er en gruppe med formel Y is a group with formula
hvori Rf, er hydrogen, metyl eller -COOR5, hvori R5er hydrogen eller lavere(Cj_4)-alkyl; Z2betyr oksygen eller -NR5-, og R7og Rg er lineær eller forgrenet alkylen med 2-10 karbonatomer, wherein R f 1 is hydrogen, methyl or -COOR 5 , wherein R 5 is hydrogen or lower (C 1-4 )-alkyl; Z2 means oxygen or -NR5-, and R7 and Rg are linear or branched alkylene with 2-10 carbon atoms,
og av fra 85 til 40 vekt-£ av en vinylmonomer (B) "bestående av en blanding av en vannoppløselig monomer B2and of from 85 to 40 wt-£ of a vinyl monomer (B) "consisting of a mixture of a water-soluble monomer B2
og en vannuoppløselig monomer , eller en vannuoppløselig monomer Bjeller en blanding herav, idet monomerene er monoolefiniske, eller en diolefinisk monomer Bxeller en blanding derav, eller en blanding av de monoolefinske og diolefinske monomere med fra 85 til 100 vekt-% av de totale monomere som vannuoppløselige, and a water-insoluble monomer, or a water-insoluble monomer Bjeller a mixture thereof, the monomers being monoolefinic, or a diolefinic monomer Bxor a mixture thereof, or a mixture of the monoolefinic and diolefinic monomers with from 85 to 100% by weight of the total monomers which water insoluble,
hvor de monoolefiniske monomerer B^er valgt blant akrylater eller metakrylater med formel CH2=CR3C00Ri2»akrylamider eller metakrylamider med formel CH2=CR3CONHRi2»maleater eller fumarater med formel Ri20C0CH=CHC00Ri2»itakonater med formel<R>i200CC:(=CH2)CH2C00R12, vinylestere med formel R12C00CH=CH2eller vinyletere med formel C02=CH0R12, idet R3betyr hydrogen eller metyl, og R^2er en lineær eller forgrenet alifatisk, cykloalifatisk eller aromatisk alkylgruppe med fra 1 til 21 karbonatomer, og som kan inneholde eter-eller tioeter-bindinger eller -CO-gruppe, eller betyr en heterocyklisk substituert alkylgruppe inneholdende oksygen-, svovel- eller nitrogenatomer, eller en polypropylenoksyd-eller poly-n-butylenoksyd-gruppe med fra 2-50 tilbakevendende alkoksyenheter eller betyr perfluorerte alkylgruper med fra 1-12 karbonatomer, eller betyr akrylonitril, styren eller cx-metylstyren, og de olefiniske monomerer B2er valgt blandt akrylater eller metakrylater med formel CH2=CR3C00R^3, akrylamider eller metakrylamider med formel CH2=CR3C0NHRi4eller CCH2=CR3C0N(R5)2, maleater eller fumarater med formel R130C0CH=CHC00R13, vinyletere med formel CH2=CH0R13, eller N-vinyllatamer, hvori R3betyr hydrogen eller metyl, R5betyr hydrogen eller lavere(Cq-4)-alkyl, R^3er et hydrokarbonre-sidu med 1-10 karbonatomer, substituert med en eller flere vannoppløseliggjørende karboksy-, hydroksy- eller tert.-aminogrupper, eller en polyetylenoksydgruppe med fra 2 til 100 tilbakevendende enheter, og R14har samme betydning som R^3eller R5, og de diolefiniske monomerer Bxer valgt blant akrylater eller metakrylater av allylalkohol, diakrylater eller dimetakrylater av rettlinjet eller forgrenet alkylenglykol med 2-6 karbonatomer, av poly(etylenoksyd)glykol, av poly(propylenoksyd)glykol, av poly(n-butylenoksyd)glykol, av where the monoolefinic monomers B^ are selected from acrylates or methacrylates with the formula CH2=CR3C00Ri2» acrylamides or methacrylamides with the formula CH2=CR3CONHRi2» maleates or fumarates with the formula Ri20C0CH=CHC00Ri2» itaconates with the formula<R>i200CC:(=CH2)CH2C00R12, vinyl esters with the formula R12C00CH=CH2 or vinyl ethers with the formula C02=CH0R12, where R3 means hydrogen or methyl, and R^2 is a linear or branched aliphatic, cycloaliphatic or aromatic alkyl group with from 1 to 21 carbon atoms, and which may contain ether or thioether bonds or -CO group, or means a heterocyclic substituted alkyl group containing oxygen, sulfur or nitrogen atoms, or a polypropylene oxide or poly-n-butylene oxide group with from 2-50 recurring alkoxy units or means perfluorinated alkyl groups with from 1-12 carbon atoms , or means acrylonitrile, styrene or cx-methylstyrene, and the olefinic monomers B2 are chosen from acrylates or methacrylates with the formula CH2=CR3C00R^3, acrylami where or methacrylamides of the formula CH2=CR3C0NHRi4or CCH2=CR3C0N(R5)2, maleates or fumarates of the formula R130C0CH=CHC00R13, vinyl ethers of the formula CH2=CH0R13, or N-vinyllatamers, in which R3 is hydrogen or methyl, R5 is hydrogen or lower (Cq- 4)-alkyl, R 3 is a hydrocarbon residue with 1-10 carbon atoms, substituted with one or more water-solubilizing carboxy, hydroxy or tert.-amino groups, or a polyethylene oxide group with from 2 to 100 recurring units, and R 14 has the same meaning as R^3 or R5, and the diolefinic monomers Bxer selected from acrylates or methacrylates of allyl alcohol, diacrylates or dimethacrylates of linear or branched alkylene glycol with 2-6 carbon atoms, of poly(ethylene oxide) glycol, of poly(propylene oxide) glycol, of poly( n-butylene oxide)glycol, av
tiodietylenglykol, av neopentylenglykol, av trimetylolpropan eller av pentaerytritol, eller reaksjonsproduktet dannet ved omsetning av 1 mol av et di- eller tri-isocyanat med strukturen OCN-(NCO)v, hvor R4har ovennevnte betydning, og v betyr 1 eller 2, med 2 eller 3 mol av et hydroksyalkylakrylat eller metakrylat. thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane or of pentaerythritol, or the reaction product formed by reacting 1 mol of a di- or tri-isocyanate with the structure OCN-(NCO)v, where R4 has the above meaning, and v means 1 or 2, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate.
Forbindelsene med strukturer (A^) og (A2> er således polysiloksaner forbundet med en diisocyanato-binding til vinylgrupper som kan være av akrylisk eller metakrylisk, fumar, eller itanon (Y struktur D), allyl (E) eller vinyleter (F) natur. The compounds with structures (A^) and (A2>) are thus polysiloxanes connected by a diisocyanato bond to vinyl groups which can be of acrylic or methacrylic, fumaric, or itanone (Y structure D), allyl (E) or vinyl ether (F) nature .
Foretrukne utførelser av foreliggende oppfinnelse har Preferred embodiments of the present invention have
= alkylen med 3 eller 4 karbonatomer, og x1 + x2= 10 til 100, = the alkylene with 3 or 4 carbon atoms, and x1 + x2 = 10 to 100,
Y1=0 til 2, Y1=0 to 2,
y2=1 til 3, y2=1 to 3,
X = -Z1-CO-CH-R4-NH-CO- X = -Z1-CO-CH-R4-NH-CO-
hvor Z^= oksygen eller -NH-f, where Z^= oxygen or -NH-f,
R^= diradikal av alifatisk eller cykloalifatisk diisocyanat med 6-10 karbonatomer, Y = av struktur D, hvori'R^= diradical of aliphatic or cycloaliphatic diisocyanate with 6-10 carbon atoms, Y = of structure D, in which'
Rg = hydrogen, Rg = hydrogen,
R8 = ~CH2CH2~ R 8 = ~CH 2 CH 2 ~
og and
Z2= oksygen eller Z2= oxygen or
Mest foretrukne utførelser omfatter polysiloksanet med struktur: (A2): Most preferred embodiments comprise the polysiloxane with structure: (A2):
r4= diradikal av isoforon-diisocyanat, r4= diradical of isophorone diisocyanate,
Zl'22= oksy9en/°9Zl'22 = oxy9ene/°9
Y2=1 eller 2. Y2=1 or 2.
Innbefattet blant de anvendelige monomerer er: metyl-; Included among the useful monomers are: methyl-;
etyl-; propyl-; isopropyl-; butyl-; isobutyl-; tert.-buty1-; ethyl-; propyl-; isopropyl-; butyl-; isobutyl-; tert.-buty1-;
etoksyetyl-; raetoksyetyl-; benzyl-; fenyl-; cykloheksyl-; ethoxyethyl-; raethoxyethyl-; benzyl-; phenyl-; cyclohexyl-;
trimetylcykloheksyl-; isobornyl-; dicyklopentadienyl-; trimethylcyclohexyl-; isobornyl-; dicyclopentadienyl-;
norbornylmetyl-; cyklododecyl-; 1,1,3,3-tetrametylbutyl-; norbornylmethyl-; cyclododecyl-; 1,1,3,3-tetramethylbutyl-;
n-butyl-; n-oktyl-; 2-etylheksyl-; decyl-; dodecyl-; tri-decyl-; oktadecyl-; glycidyl-; etyltioetyl-; furfuryl-; n-butyl-; n-octyl-; 2-ethylhexyl-; decyl-; dodecyl-; tri-decyl-; octadecyl-; glycidyl-; ethylthioethyl-; furfuryl-;
heksafluorisopropyl-; 1,1,2,2-tetrahydroperfluordodecyl-; hexafluoroisopropyl-; 1,1,2,2-tetrahydroperfluorododecyl-;
tri-, tetra- eller penta-siloksanyl propyl-akrylater og metakrylater, såvel som de tilsvarende amider; N-(l,l-dimetyl-3-oksobutyl)akrylamid; mono- og dimetylfumarat, maleat og itakonat; dietylfumarater; isopropyl og diisopro-i pylfumarat og itakonat; mono- og difenyl og metylfenyl fumarat og itakonat; metylvinyleter og metoksyetylvinyleter; tri-, tetra- or penta-siloxanyl propyl acrylates and methacrylates, as well as the corresponding amides; N-(1,1-dimethyl-3-oxobutyl)acrylamide; mono- and dimethyl fumarate, maleate and itaconate; diethyl fumarates; isopropyl and diisopropyl pylfumarate and itaconate; mono- and diphenyl and methylphenyl fumarate and itaconate; methyl vinyl ether and methoxyethyl vinyl ether;
vinylacetat, vinylpropionat, vinylbenzoat, akrylonitril, vinyl acetate, vinyl propionate, vinyl benzoate, acrylonitrile,
styren og alfa-metylstyren. styrene and alpha-methylstyrene.
) )
5 5
For å oppnå den høye klarhet som er nødvendig for kontakt-linse anvendelser, er det spesielt nyttig å anvende komonomerer eller komonomerblandinger hvis tilsvarende polymerer passer nøyaktig med oppløslighetsparameter (6) og/eller brytningsindeks (RI) av verdiene for polydimetylsiloksan (5=15; RI=1,43). Slike monomerer er f.eks. isobornyl, metakrylat, tert.-butyl-metakrylat og blandinger av hydrokarbon-metakrylater (RI 1,46) med fluor inneholdende monomerer som heksafluorisopropyl-metakrylat, trifluoretyl-metakrylat; 1,1,2,2-tetrahydroperfluoralkyl-metakrylat eller 4-tia-6-perfluoralkyl-heksyl-metakrylat, hvor alkyl eller en kar-bonkjede med 5-12 C-atomer (RI's av 1,38-1,40) (6 <15). Dessuten øker monomerer som inneholder perfluoralkyl-grupper, tydelig oksygen permeabiliteten av polymerene på en syner-gistisk måte med polysiloksan, som sådan er de derfor spesielt foretrukne komonomerer. To achieve the high clarity required for contact lens applications, it is particularly useful to use comonomers or comonomer mixtures whose corresponding polymers exactly match the solubility parameter (6) and/or refractive index (RI) of the values for polydimethylsiloxane (5=15; RI=1.43). Such monomers are e.g. isobornyl, methacrylate, tert-butyl methacrylate and mixtures of hydrocarbon methacrylates (RI 1.46) with fluorine containing monomers such as hexafluoroisopropyl methacrylate, trifluoroethyl methacrylate; 1,1,2,2-tetrahydroperfluoroalkyl methacrylate or 4-thia-6-perfluoroalkylhexyl methacrylate, where alkyl or a carbon chain of 5-12 C atoms (RI's of 1.38-1.40) ( 6 <15). Moreover, monomers containing perfluoroalkyl groups clearly increase the oxygen permeability of the polymers in a synergistic manner with polysiloxane, as such they are therefore particularly preferred comonomers.
For fremstilling av hårde linser er det foretrukne komonomer innhold 50-85 vekt-% av den totale polymer, hvorved foretrukne komonomerer er mety1-metakrylat, cykloheksyl-metakrylat, isobornyl-metakrylat, isopropyl-metakrylat, isobutyl metakrylat, tert-butyl-metakrylat eller heksafluorisopropyl-metakrylat eller blandinger derav. For the production of hard lenses, the preferred comonomer content is 50-85% by weight of the total polymer, whereby preferred comonomers are methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate or hexafluoroisopropyl methacrylate or mixtures thereof.
Det mest foretrukne komonomer er metyl-metakrylat, isobornyl metakrylat, isopropyl-metakrylat, isobutyl-metakrylat eller cykloheksyl-metakrylat, eller blandinger derav. Mest foretrukket er også blandinger av metyl-metakrylat og/eller The most preferred comonomer is methyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, isobutyl methacrylate or cyclohexyl methacrylate, or mixtures thereof. Most preferred are also mixtures of methyl methacrylate and/or
isobornyl-metakrylat med 1-2 5 vekt-% av den totale monomer av et kortkjedet kryssbindingsmiddel som neopentylenglykol-dikarylat, etylenglykol-dimetakrylat eller reaksjonsproduktet av 1 mol av isoforon-diisocyanat og 2 mol av 2-hydroksyetyl- metakrylat. isobornyl methacrylate with 1-25% by weight of the total monomer of a short-chain cross-linking agent such as neopentylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of 1 mol of isophorone diisocyanate and 2 mol of 2-hydroxyethyl methacrylate.
Et annet mest foretrukket komonomer system for fremstilling av hårde linser er vinyl-acetat/dimetyl-maleat (2/1,til 5/1 molarforhold) pluss et foretrukket metakrylat monomer Another most preferred comonomer system for making hard lenses is vinyl acetate/dimethyl maleate (2/1 to 5/1 molar ratio) plus a preferred methacrylate monomer
som angitt ovenfor. as stated above.
Por fremstilling av myke linser er det foretrukne komonomer 2-etylheksyl-akrylat, 2-etylheksyl-metakrylat, n-butyl-akrylat, n-butyl-metakrylat, n-oktyl-akrylat, n-oktyl-metakrylat, n-decyl-akrylat n-decyl metakrylat, perfluoralkyl (Cr-C,n) substituert alkyl-akrylat eller metakrylat eller blandinger derav. For the production of soft lenses, the preferred comonomer is 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate n-decyl methacrylate, perfluoroalkyl (Cr-C,n) substituted alkyl acrylate or methacrylate or mixtures thereof.
Kontaktlinsene som er fremstilt av polymerer ifølge oppfinnelsen er uten fyllstoffer, hydrolyttiske stabile, biologisk inerte, transparente og tilstrekkelig permeabel for oksygen, for å tillate transporten av tilstrekkelig oksygen for å møte behovene for den humane hornhinne. The contact lenses made from polymers according to the invention are filler-free, hydrolytically stable, biologically inert, transparent and sufficiently permeable to oxygen to allow the transport of sufficient oxygen to meet the needs of the human cornea.
Det vannoppløselige vinyl monomer (B2) som er egnet ved foreliggende oppfinnelse er fortrinnsvis akrylater og metakrylater med den generelle struktur: The water-soluble vinyl monomer (B2) which is suitable for the present invention is preferably acrylates and methacrylates with the general structure:
R,, er en hydrokarbonrest med 1-10 karbonatomer substituert R,, is a hydrocarbon residue with 1-10 carbon atoms substituted
med en eller flere vannoppløselige grupper slik som kar- with one or more water-soluble groups such as car-
5 boksy, hydroksy eller tert.-amino, eller en polyetylenoksydgruppe med fra 2-100 repeterende enheter, eller en gruppe som inneholder sulfat, fosfat, sulfonat eller fosfonat-grupper. 5 boxy, hydroxy or tert.-amino, or a polyethylene oxide group with from 2-100 repeating units, or a group containing sulphate, phosphate, sulphonate or phosphonate groups.
) Akrylamider og metakrylamider med struktur ) Acrylamides and methacrylamides with structure
> hvori R,, er R^ ellerR^; > wherein R,, is R^ or R^;
Akrylamider og metakrylamider med struktur Acrylamides and methacrylamides with structure
Maleater og fumarater med struktur Vinyletere med struktur Structured maleates and fumarates Structured vinyl ethers
N-vinyi-±aKtamater, som N-vinyi-^-pyrroxiaon, N-vinyi-±aKtamates, such as N-vinyi-^-pyrroxiaone,
Innbefattet blandt de anvendelige vannoppløselige monomerer er: Included among the applicable water-soluble monomers are:
2-hydroksyetyl-; 2- og 3-hydroksypropyl-, 2,3-dihydroksy- 2-hydroxyethyl-; 2- and 3-hydroxypropyl-, 2,3-dihydroxy-
i propyl-, polyetoksyetyl-; og polyetoksypropyl-akrylater in propyl-, polyethoxyethyl-; and polyethoxypropyl acrylates
og metakryalter såvel som de tilsvarende akrylamider og metakrylamider. Sukrose-, mannose-, glukose-, sorbi-tolakrylater og metakrylater. and methacrylates as well as the corresponding acrylamides and methacrylamides. Sucrose, mannose, glucose, sorbitol acrylates and methacrylates.
i in
i Akrylamid og metakrylamid; N-métylakrylamid og metakrylamid, bisaceton-akrylamid; 2-hydroksyetyl akrylamid; dimetylakrylamid og metakrylamid; me.tylolakrylamid og metakrylamid. i Acrylamide and methacrylamide; N-methylacrylamide and methacrylamide, bisacetone-acrylamide; 2-hydroxyethyl acrylamide; dimethylacrylamide and methacrylamide; methylacrylamide and methacrylamide.
N,N-dimetyl- og N,N-dietyl-aminoetyl-akrylat og metakrylat N,N-dimethyl and N,N-diethyl aminoethyl acrylate and methacrylate
) såvel som de tilsvarende akrylamider og metakrylamider; ) as well as the corresponding acrylamides and methacrylamides;
N-tert.butyl-aminoetyl-metakrylat og metakrylamid; 2- og' 4-vinylpyridin; 4- og 2-metyl-5-vinylpyridin; N-metyl-4-vinyl-piperidin; 1-vinyl- og 2-metyl-l-vinyl-imidazol; N-tert-butyl aminoethyl methacrylate and methacrylamide; 2- and' 4-vinylpyridine; 4- and 2-methyl-5-vinylpyridine; N-methyl-4-vinyl-piperidine; 1-vinyl- and 2-methyl-1-vinyl-imidazole;
dimetylallylamin og metyldiallylamin. Para- og orto- dimethylallylamine and methyldiallylamine. para- and ortho-
j aminostyren; dimetylaminoetyl- vinyleter; N-vinylpyrroli-don; 2-pyrrolidinoetyl-metakrylat. j aminostyrene; dimethylaminoethyl vinyl ether; N-vinylpyrrolidone; 2-pyrrolidinoethyl methacrylate.
Akryl- og metakryl-syre; itakon-; kanel-, kroton-, fumar-, maleinsyrer og lavere hydroksyalkyl mono- og diestere derav, slik som 2-hydroksyetyl- og di(2-hydroksy)etyl-fumarat, Acrylic and methacrylic acid; itakon-; cinnamic, crotonic, fumaric, maleic acids and lower hydroxyalkyl mono- and diesters thereof, such as 2-hydroxyethyl and di(2-hydroxy)ethyl fumarate,
-maleat og-itakonat, og 3-hydroksypropyl-butyl-fumarat, -maleate and itaconate, and 3-hydroxypropyl-butyl-fumarate,
og di-polyalkoksyalkyl-fumarater, maleater og itakonater. and di-polyalkoxyalkyl fumarates, maleates and itaconates.
Malein-anhydrid; natriumakrylat og metakrylat, 2-metakryla-oyloksyetylsulfonsyre, 2-akrylamido-2-metyl-propansulfon-syre, 2-fosfatetyl-metakrylat, vinylsulfonsyre, natrium-vinylsulfonat, p-styrensulfonsyre, natrium p-styrensulfonat, og allylsulfonsyre. Maleic anhydride; sodium acrylate and methacrylate, 2-methacryloyloxyethylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-phosphate ethyl methacrylate, vinylsulfonic acid, sodium vinylsulfonate, p-styrenesulfonic acid, sodium p-styrenesulfonate, and allylsulfonic acid.
Også omfattet er de kvaterniserte derivater av kationiske monomerer: oppnådd ved kvaternisering med valgte alkylerings-midler som halogenerte hydrokarboner, slik som metyljodid, benzylklorid eller heksadecyl-klorid; epoksyder som glyci-dol, epiklorhydrin, etylenoksyd; akrylsyre, dimetylsulfat; Also included are the quaternized derivatives of cationic monomers: obtained by quaternization with selected alkylating agents such as halogenated hydrocarbons, such as methyl iodide, benzyl chloride or hexadecyl chloride; epoxides such as glycidol, epichlorohydrin, ethylene oxide; acrylic acid, dimethyl sulfate;
metylsulfat; propansulton. methyl sulfate; propane sultone.
En mer fullstendig liste av vannoppløselige monomerer som er egnet i forbindelse med foreliggende oppfinnelse, finnes i: R.H. Yocum, E.B. Nyquist, Functional Monomers; vol. 1, side 424-440 (JÆ.. Dekker, N.Y. 1973 ). A more complete list of water-soluble monomers suitable in connection with the present invention can be found in: R.H. Yocum, E.B. Nyquist, Functional Monomers; Vol. 1, pages 424-440 (YÆ.. Dekker, N.Y. 1973).
Foretrukne monomerer er: Preferred monomers are:
(B^) == metyl-metakrylat, cykloheksyl^metaikrylat, isobornyl-metakrylat, t-buityl og, isobutyl-metakrylat, isopropyl-metakrylat, heksafluorisopropyl- metakrylat. (B^) == methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, t-butyl and, isobutyl methacrylate, isopropyl methacrylate, hexafluoroisopropyl methacrylate.
( B^) = 2-hydroksyetyl-metakrylat; N,N-dimetylakrylamid; (B^) = 2-hydroxyethyl methacrylate; N,N-dimethylacrylamide;
akryl og metakrylsyre, N-vinyl-2-pyrrolidon. acrylic and methacrylic acid, N-vinyl-2-pyrrolidone.
Et vidt område av divinylforbindelser kan anvendes i tillegg til monovinylforbindelsene. Fra 1-25 vekt-% av den totale monomer B kan virkelig være en diolefinisk monomer (B^). Eksempler på diolefiniske monomerer er: Allylakrylat og metakrylat, etylenglykol-, dietylen-glykol-, triet'-lenglykol-, tetraetylenglykol- og generelt polyetylen-oksyd-glykol-diakrylater og dimetakrylater; 1,4-butandiol- A wide range of divinyl compounds can be used in addition to the monovinyl compounds. From 1-25% by weight of the total monomer B can really be a diolefinic monomer (B^). Examples of diolefinic monomers are: Allyl acrylate and methacrylate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and generally polyethylene oxide glycol diacrylates and dimethacrylates; 1,4-butanediol-
og poly-n-butylen-oksyd-glykol-dikarylater og dimetakrylater; propylenglykol-og polypropylenoksyd-glykol-diakrylater og dimetakrylater; tiodietylen-glykol-diakrylat og dimetakrylat; di(2-hydroksyetyl)sulfon-diakrylat og dimetakrylat; neo-pentylen-glykol-diakrylat og dimetakrylat; trimetylolpropan-tri og tetraakrylat; pentaerythritol tri og tetraakrylat; divinylbenzen; divinyleter; divinylsulfon; disiloksanyl-bis-3-hydroksy-propyl-diakrylat eller metakrylat og beslektede forbindelser. and poly-n-butylene oxide glycol diacrylates and dimethacrylates; propylene glycol and polypropylene oxide glycol diacrylates and dimethacrylates; thiodiethylene glycol diacrylate and dimethacrylate; di(2-hydroxyethyl)sulfone diacrylate and dimethacrylate; neo-pentylene glycol diacrylate and dimethacrylate; trimethylolpropane-tri and tetraacrylate; pentaerythritol tri and tetraacrylate; divinylbenzene; divinyl ether; divinyl sulfone; disiloxanyl bis-3-hydroxy-propyl diacrylate or methacrylate and related compounds.
Bisf enol-A-diakrylat eller dimetakrylat, etoksylert-bisf enol-A-diakrylat eller dimetakrylat; metylen-bisakrylamid eller metakrylamid, dimetylen-bisakrylamid eller metakrylamid; N,N'-dihydroksyetylen-bisakrylamid eller metakrylamid; heksametylen-bisakrylamid eller metakrylamid; dekametylen-bisakrylamid eller metakrylamid; allyl- og dialkylmaleat, triallyl—melamin, diallyl-itakonat, diallyl-ftalat, triallyl-fosfinnit, polyallyl-sakkarose, sakkarose-diakrylat, glukose-dimetakrylat; også umettede polyestere, slik som poly-(alkylen-glykol^ maleater) og poly(alkylen-glykol-fumarater), som poly(propylen-glykol-maleat) og poly(polyalkylenoksyd-glykol-maleat). Bisphenol A diacrylate or dimethacrylate, ethoxylated bisphenol A diacrylate or dimethacrylate; methylene bisacrylamide or methacrylamide, dimethyl bisacrylamide or methacrylamide; N,N'-dihydroxyethylene bisacrylamide or methacrylamide; hexamethylene bisacrylamide or methacrylamide; decamethylene bisacrylamide or methacrylamide; allyl and dialkyl maleate, triallyl melamine, diallyl itaconate, diallyl phthalate, triallyl phosphinite, polyallyl sucrose, sucrose diacrylate, glucose dimethacrylate; also unsaturated polyesters, such as poly-(alkylene glycol ^ maleate) and poly(alkylene glycol fumarates), such as poly(propylene glycol maleate) and poly(polyalkylene oxide glycol maleate).
Også nyttig som kryssbindingsmidler er reaksjonsproduktene som fås ved omsetning av 1 mol av di- eller tri-isocyanat med struktur OCN-R^-(NVO)^, hvori R^ er som beskrevet nedenfor, med 2 eller 3 mol av hydroksyalkyl-akrylat eller metakrylat, eller en hydroksyalkyl-vinyleter eller allyl-al-kohol, eller N-tert.-butylaminoetyl-metakrylat, eller bis-hydroksyetyl- maleat eller hvilke som helst av de nedenfor angitte forbindelser som inneholder aktivt-hydrogen. Also useful as cross-linking agents are the reaction products obtained by reacting 1 mol of di- or tri-isocyanate of structure OCN-R^-(NVO)^, in which R^ is as described below, with 2 or 3 mol of hydroxyalkyl acrylate or methacrylate, or a hydroxyalkyl vinyl ether or allyl alcohol, or N-tert-butylaminoethyl methacrylate, or bis-hydroxyethyl maleate or any of the compounds listed below which contain active hydrogen.
Den foretrukne diolefiniske monomer (Bx) er akrylatet eller metakrylatet av allylalkohol, av en rettkjedet eller for grenet alkylenglykol med 2-6 karbonatomer, av poly(etylenoksyd)glykol, av poly(propylenoksyd)glykol, av poly(n-butylenoksyd)glykol, av tiodietylenglykol, av neopentylgly-kol, av trimetylolpropan, eller av pentaertritol; eller reaksjonsproduktet som fåes ved omsetning av 1 mol av et di- eller tri-isocyanat med struktur OCN-R4~(NCO) , hvor R. er som definert ovenfor og v er 1 eller 2, med 2 eller The preferred diolefinic monomer (Bx) is the acrylate or methacrylate of allyl alcohol, of a straight-chain or too branched alkylene glycol with 2-6 carbon atoms, of poly(ethylene oxide) glycol, of poly(propylene oxide) glycol, of poly(n-butylene oxide) glycol, of thiodiethylene glycol, of neopentyl glycol, of trimethylolpropane, or of pentaerthritol; or the reaction product obtained by reacting 1 mol of a di- or tri-isocyanate with the structure OCN-R4~(NCO) , where R. is as defined above and v is 1 or 2, with 2 or
3 mol av et hydroksyalkylakrylat eller metakrylat. 3 moles of a hydroxyalkyl acrylate or methacrylate.
En mest foretrukket difunksjonell komonomer (Bx) er 1 til 25 vekt-% av den totale monomer av neopentylenglykol-diakrylat, reaksjonsproduktet av 1 mol isoporon-diisocyanat og 2 mol av 2-hydroksyetyl-metakrylat, eller etylenglykol-dimetakrylat. A most preferred difunctional comonomer (Bx) is 1 to 25% by weight of the total monomer of neopentylene glycol diacrylate, the reaction product of 1 mol of isoporone diisocyanate and 2 mol of 2-hydroxyethyl methacrylate, or ethylene glycol dimethacrylate.
Monomerene kan anvendes alene eller i kombinasjon med hverandre hvorved det må tas den nødvendige oppmerksomhet med hensyn til deres kopolymerisasjonsparametere for å være sikker at vilkårlig kopolymerisasjon ikke finner sted. Dessuten, dersom polymerene skal anvendes for kontaktlinser, er det viktig for valg av egnet monomerkombinasjon at denne har en høy grad av klarhet og er fargeløs. The monomers can be used alone or in combination with each other whereby the necessary attention must be paid to their copolymerization parameters to ensure that arbitrary copolymerization does not take place. Moreover, if the polymers are to be used for contact lenses, it is important for the selection of a suitable monomer combination that this has a high degree of clarity and is colourless.
En foretruket utførelse av foreliggende oppfinnelse er en polymer hvor komponenten A er et polysiloksan med strukturA^eller A.,, R-^er alkylen med 3 eller 4 karbonatomer, -n. A preferred embodiment of the present invention is a polymer where the component A is a polysiloxane with structure A^ or A.,, R-^ is the alkylene with 3 or 4 carbon atoms, -n.
X er -Z1-CONH-R4-NHCO- hvor ZL -er -0- eller -NH- og X is -Z1-CONH-R4-NHCO- where ZL -is -0- or -NH- and
R4. er et diradikal av et alifatisk eller cykloalifatisk diisocyanat med 6 til 10 karbonatomer, og Y er R4. is a diradical of an aliphatic or cycloaliphatic diisocyanate of 6 to 10 carbon atoms, and Y is
hvori Rg er hydrogen, Rg er etylen, og wherein Rg is hydrogen, Rg is ethylene, and
' z2 er -0- eller -NH(CH3)3~, og komponent B inne- ' z2 is -0- or -NH(CH3)3~, and component B in-
holder fra 1-25 % basert på totalt monomer av en diolefinisk monomer (Bx) som er akrylatet eller metakrylatet av allylalkohol, av en rettkjedet eller forgrenet alkylenglykol med 2-6 karbonatomer, av poly(etylenoksyd)glykol, av poly-(propylenoksyd) glykol, av poly(n-butylenoksyd)glykol, av tiodietylenglykol, av neopentylenglykol, av trimetylolpropan, eller av pentaertyritol; eller reaksjonsproduktet som fåes ved omsetning av 1 mol av et di- eller tri-isocyanat med struktur OCN-R^-(NCO) , hvor er som definert ovenfor og v er 1 eller 2, med 2 eller 3 mol av et hydroksyalkyl-akrylat eller metakrylat. contains from 1-25% based on total monomer of a diolefinic monomer (Bx) which is the acrylate or methacrylate of allyl alcohol, of a straight-chain or branched alkylene glycol with 2-6 carbon atoms, of poly(ethylene oxide) glycol, of poly-(propylene oxide) glycol, of poly(n-butylene oxide) glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane, or of pentaerythritol; or the reaction product obtained by reacting 1 mol of a di- or tri-isocyanate with the structure OCN-R^-(NCO), where is as defined above and v is 1 or 2, with 2 or 3 mol of a hydroxyalkyl acrylate or methacrylate.
Poly- funksjonelie polysiloksaner, egnet som utgangsmateri-aier for makromeren (A), er av strukturer I eller II Polyfunctional polysiloxanes, suitable as starting materials for the macromer (A), are of structures I or II
hvori: in which:
Rl'R2'Ra'Rb'Rc'Rd'Re'Rf Rg'Rh'Ri'Rj'Rk'Zl'Rl'R2'Ra'Rb'Rc'Rd'Re'Rf Rg'Rh'Ri'Rj'Rk'Zl'
x^, * 2> vi°9^2er SOItl beskrevet ovenfor. x^, * 2> vi°9^2er SOItl described above.
Di-isocyanater egnet for dannelsen av forpolymer mellomproduktet er alifatiske, cykloalifatiske eller aroma-tiske polyisocyanater med strukturer: Diisocyanates suitable for the formation of the prepolymer intermediate are aliphatic, cycloaliphatic or aromatic polyisocyanates with structures:
og omfatter: etylen-diisocyanat, 1 ,~2-diisocyanatpropan, 1,3-diisocyanatpropan, 1,6-diisocyanatheksan, 1,2-diisocyanatcykloheksan, 1,3-diisocyanatcykloheksan, 1,4-diisocyanatcykloheksan, o-diisocyanatbenzen, m-diisocyanatbenzen, p-diisocyanatbenzen, bis(4-isocyanatcykloheksyl)metan, bis(4-iso-cyanatcykloheksanyl)metan, bis(4-isocyanatfenyl)metan, toluen- diisocyanat, 3 , 3-diklor-4 , 4 ' -diisocyanatb.i f enyl, 1,5-diisocyanatftalen, hydrert toluen-diisocyanat, and includes: ethylene diisocyanate, 1,~2-diisocyanate propane, 1,3-diisocyanate propane, 1,6-diisocyanate hexane, 1,2-diisocyanate cyclohexane, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, o-diisocyanatebenzene, m- diisocyanatebenzene, p-diisocyanatebenzene, bis(4-isocyanatecyclohexyl)methane, bis(4-isocyanate cyclohexanyl)methane, bis(4-isocyanatephenyl)methane, toluene diisocyanate, 3,3-dichloro-4,4'-diisocyanateb.if f enyl, 1,5-diisocyanatephthalein, hydrogenated toluene diisocyanate,
l-isocyanatmetyl-5-isocyanat-l,3,3-trimetylcyklo- 1-isocyanatemethyl-5-isocyanate-1,3,3-trimethylcyclo-
i heksan (= isoforan-diisocyanat), 1,6-diisocyannt-2,24-(2,4,4)-trismetylheksan, 2,2'-diisocyanatdietyl fumarat, 1,5-diisocyanat-I-karboksypentan, in hexane (= isophorane diisocyanate), 1,6-diisocyanate-2,24-(2,4,4)-trismethylhexane, 2,2'-diisocyanate diethyl fumarate, 1,5-diisocyanate-1-carboxypentane,
1„,2-, 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 1„,2-, 1,3-, 1,5-, 1,6-, 1,7-, 1,8-,
2,7- og 2,3-diisocyairatnaftalen; 2,4- og 2,7-diisocyanat- 2,7- and 2,3-diisocyanate naphthalene; 2,4- and 2,7-diisocyanate
i 1-metylnaftalen; 1,4-diisocyanat-metyl-cykloheksan; 1,3-diisocyanat-6 ( 7 ) -metyln-af talen; 4,4' -diisocyanatbif enyl ; in 1-methylnaphthalene; 1,4-diisocyanate-methyl-cyclohexane; 1,3-diisocyanate-6(7)-methyln-aphthalene; 4,4'-diisocyanate biphenyl;
4,4'-diisocyanat-3,3æ-dimetoksy-bisfenyl; 3,3'- og 4,4'-diisocyanat-2,2<1->dimetyl bifenyl; Bis-(4-isocyanatfenyl)etan; 4,4'-diisocyanate-3,3α-dimethoxy-bisphenyl; 3,3'- and 4,4'-diisocyanate-2,2<1->dimethyl biphenyl; Bis-(4-isocyanatephenyl)ethane;
bis(4-isocyanatfenyl)eter. bis(4-isocyanatephenyl)ether.
) )
Diisocyanatene kan anvendes alene eller i kombinasjon med hverandre. The diisocyanates can be used alone or in combination with each other.
Aktiv hydrogen- innholdende monomerer egnet for å endeavslutte 5 polysiloksan-polyisocyanatet omfatter forbindelser med strukturen: Active hydrogen-containing monomers suitable for terminating 5 the polysiloxane-polyisocyanate include compounds with the structure:
hvori R^, Rg, Rg, og Z«er som beskrevet ovenfor og som sådanne er aktiv hydrogeninnholdende akrylater, metakrylater, fumarater, maleater og de tilsvarende amider, slik som: 2-hydroksyetyl-; og 3-hydroksypropyl-; 2,3-dihydroksypropyl-; polyetoksyetyl-; polyetoksypropyl-; polypropoksy-propy-1-akrylater og metakrylater såvel som de tilsvarende akrylyl-og metakrylamider; 2-hydroksyetyl oq bis(2-hydroksyetvl)-fumarat, hydroksypropylbutyl-fumarat; N-(2-hydroksyetyl)maleimid og N-(2-hydroksyetoksy-etyl)maleimid; tert.-butylaminoetyl-metakrylat , pentaerytritol mono-, in which R^, Rg, Rg, and Z' are as described above and as such are active hydrogen-containing acrylates, methacrylates, fumarates, maleates and the corresponding amides, such as: 2-hydroxyethyl-; and 3-hydroxypropyl-; 2,3-dihydroxypropyl-; polyethoxyethyl-; polyethoxypropyl-; polypropoxy-propyl-1-acrylates and methacrylates as well as the corresponding acrylyl and methacrylamides; 2-hydroxyethyl oq bis(2-hydroxyethyl)fumarate, hydroxypropylbutyl fumarate; N-(2-hydroxyethyl)maleimide and N-(2-hydroxyethoxyethyl)maleimide; tert-butylaminoethyl methacrylate, pentaerythritol mono-,
og diakrylat. and diacrylate.
Andre egnede klasser av forbindelser er allyl-monomerer slik som allylalkohol og metallylalkohol og diallylamin; Other suitable classes of compounds are allyl monomers such as allyl alcohol and methallyl alcohol and diallylamine;
og and
vinyletaner med strukturen vinylethanes with the structure
hvor R^er som beskrevet ovenfor, f.eks. 4-hydroksybutyl-vinyleter. where R^ is as described above, e.g. 4-hydroxybutyl vinyl ether.
En liste av egnede monomerer i forbindelse med denne oppfinnelse finnes i R.H. Yocum, E.B. Nyguist; Functional Monomers, vol. 1, sider 424-440 (M. Dekker, N.Y. 1973). A list of suitable monomers in connection with this invention can be found in R.H. Yocum, E.B. New Guist; Functional Monomers, vol. 1, pages 424-440 (M. Dekker, N.Y. 1973).
Polysiloksan-polyisocyanat-forpolymeren kan også endeavsluttes av umettede syrer ved anvendelse av en base eller metallkatalysator og resultere i en amidbinding med utvik-ling av CC>2 • Egnede syrer omfatter: akrylsyre, metakryl- syre, fumarsyre, maleinsyre, itakonsyre, kanlesyre. The polysiloxane-polyisocyanate prepolymer can also be end-capped by unsaturated acids using a base or metal catalyst and result in an amide bond with the development of CC>2 • Suitable acids include: acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid.
Monomerene og B^, diisocyanatene og de poly-funksjonelle polysiloksan utgangsmaterialer for A er i stor utstrekning produkter som finnes i handelen. The monomers and B^, the diisocyanates and the polyfunctional polysiloxane starting materials for A are largely commercially available products.
Polysiloksan makromerene fåes vanligvis ved en 2-trinns syntese fra de tilsvarende polyfunksjonelle polysiloksaner. Disse er i det mest foretrukne tilfelle dioler eller poly-oler, men kan også være amino-funksjonelle eller merkapto-funksjonelle polysiloksaner. Som et første trinn omsettes polysiloksanet, enten i bulk eller i oppløsning, med en gitt mengde av et di- eller tri-isocyanat i nærvær av hvilken som helst av de konvensjonelle katalysatorer. Denne katalysator kan være forbindelser som inneholder tertiære aminogrupper slik som trietylamin, pyridin eller diamino-bicyklooktan, eller metall-baserte lysatorer som dibutyl-tinndilaurat eller tinnoktoat. Omsetningen utføres enten ved omgivelsestemperaturer eller forhøyede temperaturer under en tørr nitrogen atmosfære og kan følges konvensjonelt med et NCO-titrering eller IR-analyse. I tilfelle av diisocyanat minsker % NCO til en beregnet verdi av den opp-rinnelige verdi, og det første trinns reaksjonsprodukt består av et polysiloksan diisocyanat. Det molare forhold av OH til NCO grupper under det første reaksjonstrinn kan være 1:1,5 til 1:3 og er fortrinnsvis i området av 1:2,05-1:2,1. The polysiloxane macromers are usually obtained by a 2-step synthesis from the corresponding polyfunctional polysiloxanes. These are in the most preferred case diols or polyols, but can also be amino-functional or mercapto-functional polysiloxanes. As a first step, the polysiloxane is reacted, either in bulk or in solution, with a given amount of a di- or tri-isocyanate in the presence of any of the conventional catalysts. This catalyst can be compounds containing tertiary amino groups such as triethylamine, pyridine or diamino-bicyclooctane, or metal-based lysators such as dibutyl tin dilaurate or tin octoate. The reaction is carried out either at ambient temperatures or elevated temperatures under a dry nitrogen atmosphere and can be followed conventionally with an NCO titration or IR analysis. In the case of diisocyanate, the % NCO decreases to a calculated value of the initial value, and the first stage reaction product consists of a polysiloxane diisocyanate. The molar ratio of OH to NCO groups during the first reaction step can be 1:1.5 to 1:3 and is preferably in the range of 1:2.05-1:2.1.
Det andre trinn av omsetningen består av endeavslutning The second stage of the turnover consists of closing
av dette poly-isocyanat med en hydroksy- eller amino-funksjonell vinylforbindelse, mest vanlig med 2-hydroksyetyl-metakrylat. Det er tilrådelig å anvende i det minste et lite overskudd av den ende-avsluttende monomer, typisk et mol-forhold av OH, SH, NH/NCO på 1,05/1 eller større. of this polyisocyanate with a hydroxy- or amino-functional vinyl compound, most commonly with 2-hydroxyethyl methacrylate. It is advisable to use at least a small excess of the end-terminating monomer, typically a mole ratio of OH, SH, NH/NCO of 1.05/1 or greater.
Da det er en foretrukket praksis å innarbeide mindre mengder av en vannoppløselig monomer i sluttpolymeren for å oppnå gode fukteegenskaper, er et større overskudd av den hydroksy- eller aminofunksjonelle monomer ikke ugunstig. Reaksjonen forløper ved omgivelses- eller forhøyede temperaturer under en periode av flere timer, hvor en ytterligere katalysator ikke er nødvendig. Da vanligvis ingen inhibitorer er tilstede, er det viktig med en oksygen-fri , nitrogen-atmosf ære. Avslutningen av reaksjonen bestemmes lett med IR spektroskopi hvor -NCO grupper'kontrolleres. As it is a preferred practice to incorporate smaller amounts of a water-soluble monomer in the final polymer in order to achieve good wetting properties, a larger excess of the hydroxy- or amino-functional monomer is not unfavorable. The reaction proceeds at ambient or elevated temperatures over a period of several hours, where an additional catalyst is not necessary. As usually no inhibitors are present, it is important to have an oxygen-free, nitrogen atmosphere. The completion of the reaction is easily determined by IR spectroscopy where -NCO groups are checked.
Noen ganger er det praktisk, f.eks. i tilfeller av meget Sometimes it is convenient, e.g. in cases of very
høy viskosemateriale, å utføre det andre trinn av makromer-syntesen i en monomer oppløsning som tilsvarer til den ønskede sluttpolymer sammensetning. Skjønt det er foretrukket å omsette et ekvivalent reaktivt polysiloksan med nær til to ekvivalenter diisocyanat og derved oppnå et isocyanat-endeavsluttet polysiloksan, kan det på grunn av lovene om polykondensasjonskinetikk fåes en bestemt mengde av kjedeforlenget produkt, i hvilket det endeavsluttede polymer inneholder to polysiloksankjeder bundet av en diisocyanatenhet, high viscose material, to carry out the second step of the macromer synthesis in a monomer solution corresponding to the desired final polymer composition. Although it is preferred to react one equivalent of reactive polysiloxane with close to two equivalents of diisocyanate and thereby obtain an isocyanate-terminated polysiloxane, due to the laws of polycondensation kinetics, a certain amount of chain-extended product can be obtained, in which the end-terminated polymer contains two polysiloxane chains bound of a diisocyanate unit,
og kan analyseres, f.eks. ved gelgjennomtrengningskromatografi. and can be analyzed, e.g. by gel permeation chromatography.
Det er også innen rammen av foreliggende oppfinnelse å anvende som polysiloksaner for polymerer dannet fra polysiloksaner med strukturer I og II ved kjede-forlengende reaksjoner som vanligvis anvendes av fagmannen innen polykon-densasjons-,spesielt polyuretan, kjemi. Slike kjedeforlengelser kan utføres f.eks. ved polykondensasjon av de ovenfor nevnte polysiloksandioler, ditioler eller diaminer med: disyrelorider eller anhydrider eller dianhydrider, slik som teraftaloylklorid, adipinsyre diklorid, maleinanhydrid, ftalanhydrid eller benzofenon-tetrakarboksylsyre og dian-hydrid, med diisocyanater med strukturer som ovenfor nevnt, It is also within the scope of the present invention to use as polysiloxanes for polymers formed from polysiloxanes with structures I and II by chain-extending reactions which are usually used by those skilled in the field of polycondensation, especially polyurethane, chemistry. Such chain extensions can be carried out e.g. by polycondensation of the above-mentioned polysiloxanediols, dithiols or diamines with: diacid chlorides or anhydrides or dianhydrides, such as teraphthaloyl chloride, adipic acid dichloride, maleic anhydride, phthalic anhydride or benzophenone tetracarboxylic acid and dianhydride, with diisocyanates with structures as mentioned above,
i hvilke tilfelle syntesetrinnet for fremstilling av det NCO-endeavsluttede makromer som beskrevet, utføres enkelt med et mindre enn et 2:1 overskudd av NCO i forhold til -OH, -SH eller -NH2gruppe, likeledes kan de NCO-endestående forpolymerer, dannet før slutt-endeavslutningen, in which case the synthesis step for the preparation of the NCO-terminated macromer as described is easily carried out with less than a 2:1 excess of NCO relative to -OH, -SH or -NH2 groups, likewise the NCO-terminated prepolymers, formed before the end-end-end,
utføres med hydroksy-vinyl forbindelsene- kjedeforlengelse med dioler eller diaminer i henhold til den kjente teknikk fra polyuretanteknologi, med, f.eks., etylenglykol, propylenglykol, butandiol, heksandiol, polyeterdioler inneholdende etylenoksyd, propylenoksyd eller n-butylenoksyd repeterende enheter? polyesterdioler, etylendiamin, heksandiamin og diprimære eller di-sekundære aminer generelt, omfattende diaminer avledet fra polyalkylenoksyder. I avhengighet av graden av disse kjedeforlengelses-reaksjoner av ytterligere amid, uretan eller ureagrupper som innføres i strukturen, bidrar de ved hydrogen-binding til stivhet og klarhet av polymeren. Kjedeforlengelser av den art som nettopp er beskrevet ovenfor, fortynner imidlertid det totale polysiloksan-innhold av forpolymeren og derfor er det større mengder av et slikt forpolymer nødvendig for å opprettholde en høy oksygenpermeabilitet i sluttpolymeren. is carried out with the hydroxy-vinyl compounds - chain extension with diols or diamines according to the known technique from polyurethane technology, with, for example, ethylene glycol, propylene glycol, butanediol, hexanediol, polyetherdiols containing ethylene oxide, propylene oxide or n-butylene oxide repeating units? polyester diols, ethylenediamine, hexanediamine and diprimary or di-secondary amines in general, including diamines derived from polyalkylene oxides. Depending on the degree of these chain extension reactions of additional amide, urethane or urea groups introduced into the structure, they contribute by hydrogen bonding to the stiffness and clarity of the polymer. However, chain extensions of the kind just described above dilute the total polysiloxane content of the prepolymer and therefore larger amounts of such a prepolymer are required to maintain a high oxygen permeability in the final polymer.
De transparente, hårde og oksygenpermeable polymerer ifølge oppfinnelsen fremstilles i et sluttsyntesetrinn ved fri radikal kopolymerisasjon, enten i bulk eller i nærvær av mindre mengder av oppløsningsmidlet. Nevnte syntesetrinn for fremstilling av en kopolymer er en fremgangsmåte som innbe-fatter omsetning av polysiloksanforbindelser med formel The transparent, hard and oxygen-permeable polymers according to the invention are produced in a final synthesis step by free radical copolymerization, either in bulk or in the presence of smaller amounts of the solvent. Said synthesis step for the production of a copolymer is a method which includes reacting polysiloxane compounds with the formula
eller or
hvori Rlf R2, Ra,<R>b, Rc, Rd>Re, Rf>Rg>Rh>Rl><R>jf<R>k> Zi( xl'x2'yi °S v2nar de 1 krav 1 angitte betydninger, wherein Rlf R2, Ra,<R>b, Rc, Rd>Re, Rf>Rg>Rh>Rl><R>jf<R>k> Zi( xl'x2'yi °S v2nar the 1 claim 1 specified meanings ,
med diisocyanater med formel with diisocyanates of formula
hvori R4har den i krav 1 angitte betydning, i nærvær av en katalysator, idet de resulterende polysiloksan-polyisocyanat-prepolymerene endedekkes ved å omsette dem med et lite overskudd av aktiv hydrogenholdig monomere med formel wherein R4 has the meaning stated in claim 1, in the presence of a catalyst, the resulting polysiloxane-polyisocyanate prepolymers being end-capped by reacting them with a small excess of active hydrogen-containing monomers of the formula
hvori in which
R3, Rfc, Rg og Z2har de i krav 1 angitte betydninger, eller med allylalkohol eller metallylalkohol eller forbindelser med formel R3, Rfc, Rg and Z2 have the meanings stated in claim 1, or with allyl alcohol or methallyl alcohol or compounds of the formula
hvori in which
R7har den i krav 1 angitte betydning, for således å danne polysiloksanmakromerene (A) som kopolymeriseres med en vinylmonomer (B), valgt fra en blanding av en vannoppløselig monomer B2og en vannuoppløselig' monomer B^, en vannuopp-løselig monomer Bj , eller en blanding herav, idet monomerene er monoolefiniske, en diolefinisk monomer Bxeller en blanding herav, eller en blanding av monoolefiniske monomerer og diolefiniske monomerer, idet den monomere har betydningen angitt i krav 1, idet det benyttes en fri radikalutviklende initiator.Polymerisasjonen utføres passende ved oppvarming og passende i nærvær av en fri radikal frembringende initiator, f.eks. ved en temperatur i området fra ca. 40°C til ca. 105°C i foretrukne temperatur-områder er mellom ca. 50°C og ca. 100°C. Disse initiatorer er fortrinnsvis peroksyder eller azokatalysatorer som har en halveringstid ved polymerisasjonstemperaturen på i det minste 20 minutter. Typiske egnede peroksyd-forbindelser omfatter: isopropylperkarbonat, tert-butyl peroktoat, benzoyl peroksyd, lauroylperoksyd, decanoylperoksyd, acetylperoksyd, ravsyreperoksyd, metyletylketonperoksyd, tert.-butylperoksy-acetat, propionylperoksyd, 2,4-diklorbenzoylperoksyd, tert-butyl peroksypivalat, pelargonylperoksyd, 2,5-dimetyl-2,5-bis(2-etylheksanoylperoksy)heksan, p-klorbenzoyl peroksyd, tert.-butyl peroksybutyrat, tert.-butyl peroksymaleinsyre, tert.-butyl-peroksyisopropylkarbonat, bis(1-hydroksycykloheksyl)peroksyd, azo forbindelser omfattende: 2,2-azo-bis-isobutyronitril, 2,2'-azo-bis(2,4-dimetylvaleronitril), l,l'-azo-bis(cykloheksankarbonitril), 2,2'-azo-bis(2,4-dimetyl-4-metoksyvaleronitril). R7 has the meaning stated in claim 1, so as to form the polysiloxane macromers (A) which are copolymerized with a vinyl monomer (B), selected from a mixture of a water-soluble monomer B2 and a water-insoluble monomer B^, a water-insoluble monomer Bj, or a mixture thereof, the monomers being monoolefinic, a diolefinic monomer Bxor a mixture thereof, or a mixture of monoolefinic monomers and diolefinic monomers, the monomer having the meaning stated in claim 1, using a free radical developing initiator. The polymerization is suitably carried out by heating and suitably in the presence of a free radical producing initiator, e.g. at a temperature in the range from approx. 40°C to approx. 105°C in preferred temperature ranges are between approx. 50°C and approx. 100°C. These initiators are preferably peroxides or azo catalysts which have a half-life at the polymerization temperature of at least 20 minutes. Typical suitable peroxide compounds include: isopropyl percarbonate, tert-butyl peroctoate, benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, acetyl peroxide, succinic peroxide, methyl ethyl ketone peroxide, tert-butyl peroxyacetate, propionyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxy pivalate, pelargonyl peroxide, 2 ,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, p-chlorobenzoyl peroxide, tert-butyl peroxybutyrate, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate, bis(1-hydroxycyclohexyl)peroxide, azo compounds comprising: 2,2-azo-bis-isobutyronitrile, 2,2'-azo-bis(2,4-dimethylvaleronitrile), 1,1'-azo-bis(cyclohexanecarbonitrile), 2,2'-azo-bis( 2,4-dimethyl-4-methoxyvaleronitrile).
Andre frie radikal-frembringende mekanismer kan anvendes, slik som stråling med f.eks. røntgenstråler, elektron-stråler og UV-stråling. Fremstilling av kontakt-linse råemner ved hjelp av UV-stråling i nævær av en foto-initiator, slik som dietoksyacetofenon, 1-hydroksycykloheksyl-fenylketon, 2,2-dimetoksy-2-fenylacetofenon, fenotiazin, diisopropyl-xanthogendisulfid, benzoin og benzoin derivater er en foretrukket fremgangsmåte. Other free radical-producing mechanisms can be used, such as radiation with e.g. X-rays, electron beams and UV radiation. Production of contact lens raw materials using UV radiation in the presence of a photo-initiator, such as diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2,2-dimethoxy-2-phenylacetophenone, phenothiazine, diisopropyl-xanthogen disulphide, benzoin and benzoin derivatives is a preferred method.
Mengden av initiator kan variere fra 0,002% til 1 vekt-% The amount of initiator can vary from 0.002% to 1% by weight
av monomeren og makromeren, men er fortrinnsvis fra 0,03 of the monomer and the macromer, but is preferably from 0.03
til 0,3 vekt-% derav. to 0.3% by weight thereof.
En foretrukket laboratoriemetode for fremstilling av polymeren, i form av en sylinder, omfatter fylling av en elas-tisk polymer sylinder: med den foretrukne sammensetning av makromer,. monomerer og katalysator, og omsetning av blandingen i ca.. 2 timer ved- 80°C. Den ferdige artikkel fjernes ved å spalte sylinderen på langs og strippe den vekk fra polymer ar ikke len:. A preferred laboratory method for producing the polymer, in the form of a cylinder, comprises filling an elastic polymer cylinder: with the preferred composition of macromers. monomers and catalyst, and reacting the mixture for approx. 2 hours at 80°C. The finished article is removed by splitting the cylinder lengthwise and stripping it away from the polymer.
Enanne.^. foretrukket fremgangsmåte for fremstilling av polymeren, er ved bestråling med ultrafiolett lys i nærvær av en f oto-ij^itiator og anvendelse av plastformer som er trans-parent for UV, slik som former fremstilt av polypropylen. Omsetningen utføres fortrinnsvis i en inert atmosfære dersom utført i åpne former. Det er kjent at oksygen inhiberer polymerisasjon og gir årsak til utvidet polymerisasjonstid.. Dersom lukkede former anvendes for å danne artikkelen, er formene sammensatt av inerte materialer som har lav oksygen-permeabilitet og ikke-klebende egenskaper. Eksempler på egnede form-materialer, er poly(tetrafluoretylen), slik som Teflon, silikongummi, polyetylen, polypropylen og poly-ester, slik som Mylar. Glass- og metallformer kan benyttes dersom det anvendes et egnet form-slippe-middel. Enanne.^. preferred method for producing the polymer is by irradiation with ultraviolet light in the presence of a photo-initiator and the use of plastic forms which are transparent to UV, such as forms made of polypropylene. The reaction is preferably carried out in an inert atmosphere if carried out in open forms. It is known that oxygen inhibits polymerization and causes extended polymerization time. If closed molds are used to form the article, the molds are composed of inert materials that have low oxygen permeability and non-adhesive properties. Examples of suitable mold materials are poly(tetrafluoroethylene), such as Teflon, silicone rubber, polyethylene, polypropylene and polyester, such as Mylar. Glass and metal molds can be used if a suitable mold release agent is used.
De transparente og oksygenpermeable polymerer i henhold The transparent and oxygen-permeable polymers according
til oppfinnelsen består av 8-70% av makromeren (A), kopolymerisert med 30-92% av vinylkomonomer komponenten (B). to the invention consists of 8-70% of the macromer (A), copolymerized with 30-92% of the vinyl comonomer component (B).
Polymerene ifølge oppfinnelsen kan tilpasses slik at de The polymers according to the invention can be adapted so that they
er egnet enten som hård kontaktlinse-materiale eller som myk kontaktlinse-materiale. Forskjellige komonomerer og forskjellige mengder av polysiloksan makromer kreves for å oppnå optimal utførelse ved den ene eller andre kontakt-linse-type. is suitable either as hard contact lens material or as soft contact lens material. Different comonomers and different amounts of polysiloxane macromers are required to achieve optimal performance with one or the other contact lens type.
Ved valg av polysiloksan komponenten og vinylmonomeren for en hård kontaktlinse-sammensetning er det naturligvis viktig å finne frem til en blanding som vil gi klare polymerer med tilstrekkelig mol stabilitet og oksygen-permeabilitet. Noen ganger er en blanding av komonomerer fordelaktig for When choosing the polysiloxane component and the vinyl monomer for a hard contact lens composition, it is naturally important to find a mixture that will give clear polymers with sufficient molecular stability and oxygen permeability. Sometimes a mixture of comonomers is advantageous
å unngå fase-separasjon og dermed opasitet. Det er også lettere å oppnå klare produkter med polysiloksaner med rela-tivt lav molekylvekt enn med høy molekylvekt polysiloksan. Polysiloksaner med en kort kjedelengde mellom kryssbindinger gir også hårdere, mer mol-stabile polymerer, men deres oksygenpermeabilitet er redusert i sammenligning med polysilok-1 saner med lengre kjedelengde og derfor lavere kryssbindings-densitet. Ved en skjønnsomt valg av monomer(er) og polysiloksan makromer er en istand til å tilpasse til en betrakte- to avoid phase separation and thus opacity. It is also easier to obtain clear products with relatively low molecular weight polysiloxanes than with high molecular weight polysiloxane. Polysiloxanes with a short chain length between crosslinks also give harder, more molally stable polymers, but their oxygen permeability is reduced compared to polysiloxanes with longer chain length and therefore lower crosslink density. With a judicious choice of monomer(s) and polysiloxane macromers, it is possible to adapt to a consider-
lig grad i fysikalske verdier og oksygen permeabilitet av silikonpolymerene. equal degree in physical values and oxygen permeability of the silicone polymers.
For fremstilling av hårde kontaktlinser, omfatter den foretrukne polymer det kryssbundne kopolymerisasjonsprodukt av (A) fra ca. 15 til ca. 35 vekt-% av en polysiloksan makromer, og (B) fra ca. 80 til ca. 65 vekt-% av en blanding For the manufacture of hard contact lenses, the preferred polymer comprises the cross-linked copolymerization product of (A) from about 15 to approx. 35% by weight of a polysiloxane macromer, and (B) from approx. 80 to approx. 65% by weight of a mixture
av vann-uoppløselige monomerer (B^), av vann-oppløselige monomerer (B2), og en diolefinisk monomer (Bx), hvori, basert på vekst-% av den totale vekt av monomerer, B^er fra ca. 60 til ca. 95%, B2er fra ca. 15 til ca. 0%, og B^ er fra ca. 25 til ca. 5%. De foretrukne vann-uoppløselige monomerer B^ er metylmetakrylat, isopropyl-metakrylat, isobutyl-metakrylat, tert-butyl-metakrylat, cykloheksyl-metakrylat, isobornyl-metakrylat eller blandinger derav. De foretrukne vann-oppløselige monomerer B2er 2-hydroksyetyl-metakrylat, N,N-dimetylakrylamid, akrylsyre, metakrylsyre eller N-vinyl-2-pyrrolidon eller blandinger derav. Den foretrukne diolefiniske monomer B^ er neopentylenglykol-diakrylat, etylenglykol-dimetakrylat eller reaksjonsproduktet av 1 mol av isoforon-diisocyanat og 2 mol av 2-hydroksyetyl-metakrylat. of water-insoluble monomers (B^), of water-soluble monomers (B2), and a diolefinic monomer (Bx), wherein, based on growth % of the total weight of monomers, B^ is from ca. 60 to approx. 95%, B2s from approx. 15 to approx. 0%, and B^ is from approx. 25 to approx. 5%. The preferred water-insoluble monomers B1 are methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate or mixtures thereof. The preferred water-soluble monomers B2 are 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid or N-vinyl-2-pyrrolidone or mixtures thereof. The preferred diolefinic monomer B1 is neopentylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of 1 mole of isophorone diisocyanate and 2 moles of 2-hydroxyethyl methacrylate.
For fremstilling av myke kontaktlinser, omfatter det foretrukne polymer-kryssbindings-kopolymerisasj onsproduktet av (A) fra ca. 40 til ca. 60 vekt-% av en polysiloksan makromer, og (B) fra ca. 60 til ca. 40 vekt-% av en blanding av vann-uoppløselig monomer (B^, av vann-oppløselig monomer (B2), og av en diolefinisk monomer (B^), hvori, basert på vekt-% av den totale vekt av monomerer, B^er fra ca. For making soft contact lenses, the preferred polymer crosslink copolymerization product of (A) comprises from about 40 to approx. 60% by weight of a polysiloxane macromer, and (B) from approx. 60 to approx. 40% by weight of a mixture of water-insoluble monomer (B^, of water-soluble monomer (B2), and of a diolefinic monomer (B^), wherein, based on the weight% of the total weight of monomers, B ^is from approx.
75 til ca. 100%, B2er- fra ca. 25 til ca. 0%, og Bxer fra ca. 5 til ca. 0%. De foretrukne vann-uoppløselige monomerer (B^) er etylakrylat eller metakrylat, n-butylakrylat eller metakrylat, n-heksylakrylat eller metakrylat, 2-etylheksyl-akrylat eller metakrylat, n-oktyl-akrylat eller metakrylat, n-decylakrylat eller metakrylat, eller blandinger derav eller med blandinger derav med metyl eller isobornyl-met- 75 to approx. 100%, B2er- from approx. 25 to approx. 0%, and Bxer from approx. 5 to approx. 0%. The preferred water-insoluble monomers (B^) are ethyl acrylate or methacrylate, n-butyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decyl acrylate or methacrylate, or mixtures thereof or with mixtures thereof with methyl or isobornyl-meth-
akrylat. De foretrukne vann-oppløselige monomerer (B2) acrylate. The preferred water-soluble monomers (B2)
og diolefiniske monomerer (Bx) er de som er angitt ovenfor for fremstilling av hårde kontaktlinser. and diolefinic monomers (Bx) are those indicated above for making hard contact lenses.
Et eksempel på en foretrukket polymer for fremstilling av An example of a preferred polymer for the manufacture of
en hård kontaktlinse omfatter (A) 30 vekt-% av polysiloksanet med struktur A2, hvor R4er et diradikal avledet fra iso-forondiisocyanat, Z, og Zp er hver -0-, og y„ er 2, og 70 vekt-% av monomer (B) hvori, basert på vekt-% av totale monomerer, B^er 71,4% av metylrnetakrylat, B2er 5,7% av 2-hyroksyetylmetakrylat og Bxer 22,9% av neopentylenglykol-diakrylat. a hard contact lens comprises (A) 30% by weight of the polysiloxane of structure A2, where R4 is a diradical derived from isophorone diisocyanate, Z, and Zp are each -0-, and y„ is 2, and 70% by weight of monomer (B) wherein, based on % by weight of total monomers, B is 71.4% of methyl methacrylate, B2 is 5.7% of 2-hydroxyethyl methacrylate, and Bx is 22.9% of neopentylene glycol diacrylate.
Et eksempel på en foretrukket polymer for å fremstille en myk kontaktlinse omfatter (A) 50 vekt-% av polysiloksanet med struktur A2 hvor R4er et diradikal utledet fra isoforon-diisocyanat, Z-^og Z2er hver -O-, og y2er 2, og 50 vekt-% av monomerer (B) hvori B^er 80% av en 50/50 blanding av metylmetakrylat/2-etylheksylakrylat og B2er 20% An example of a preferred polymer for making a soft contact lens comprises (A) 50% by weight of the polysiloxane of structure A2 where R4 is a diradical derived from isophorone diisocyanate, Z-^ and Z2 are each -O-, and y2 is 2, and 50% by weight of monomers (B) in which B^ is 80% of a 50/50 mixture of methyl methacrylate/2-ethylhexyl acrylate and B2 is 20%
av 2-hydroksyetyl-metakrylat. of 2-hydroxyethyl methacrylate.
Skjønt oppfinnelsen er rettet primært mot fremstilling av hårde, dimensjonsstabile kontaktlinser, er det innen rammen av oppfinnelsen å anvende hvilke som helst av de ovenfor nevnte monomerer for å fremstille sterke, 02-permeable polymerer med et vidt område av fysiske verdier, fra hård og stiv til gummiaktig og myk. Slike myke polymerer er f.eks. egnet for bandasjer, eller som myke kontaktlinser, spesielt når de er behandlet med et hvilket som helst av de vanlige anvendte metoder som anvendes for å øke fukteevnen av hydrofobe overflater, slik som plasma-behandling og stråle-for-edling og oksydasjon. Although the invention is directed primarily to the production of hard, dimensionally stable contact lenses, it is within the scope of the invention to use any of the above-mentioned monomers to produce strong, 02-permeable polymers with a wide range of physical values, from hard and rigid until rubbery and soft. Such soft polymers are e.g. suitable for dressings, or as soft contact lenses, especially when treated by any of the commonly used methods used to increase the wettability of hydrophobic surfaces, such as plasma treatment and beam refining and oxidation.
På grunn av deres gode vevsforenlighet og oksygen permeabilitet og styrke og elastisitet, er polymerene i henhold til foreliggende oppfinnelse spesielt egnet for anvendelse som intra-muskulære og subkutane implantanter i varmblodige dyr og som kontaktlinsemateriale. For samme grunner, kan materialene i henhold til foreliggende oppfinnelse, tilpasses til erstatnings-blodkar eller ektrakorpolige shunter. Due to their good tissue compatibility and oxygen permeability and strength and elasticity, the polymers according to the present invention are particularly suitable for use as intramuscular and subcutaneous implants in warm-blooded animals and as contact lens material. For the same reasons, the materials according to the present invention can be adapted to substitute blood vessels or extracorporeal shunts.
De følgende eksempler bestemmer spesifikt oksygen-perrneabili-tet (02.DK) ved måling av oppløse oksygen-permeabilitet ved 35°C med en polarografisk elektrode i en luft-mettet vandig omgivelse og uttrykkes i enheter The following examples specifically determine oxygen permeability (02.DK) by measuring dissolved oxygen permeability at 35°C with a polarographic electrode in an air-saturated aqueous environment and are expressed in units
Fukteevne bestemmes ved måling av kontaktvinkelen på en n-oktan tråle som hadde steget til den lavere overflate av et 1 mm tykt prøveark dyppet i oktan mettet med destillert vann ved 36°C. Ved denne måling angir høye tall høy fukteevne. Wetting ability is determined by measuring the contact angle of an n-octane trawl that had risen to the lower surface of a 1 mm thick test sheet dipped in octane saturated with distilled water at 36°C. In this measurement, high numbers indicate high wetting ability.
Hårdhet betemmes ved anvendelse av et shore-D durometer Hardness is determined using a shore-D durometer
på polerte overflater av senterskjærte knapper med 10 mm diameter og 8 mm høyde. on polished surfaces of center-cut buttons with a diameter of 10 mm and a height of 8 mm.
Eksempel 1. Example 1.
Fremstilling av poly- siloksan makromer. Production of polysiloxane macromers.
En 1-liters 3-hals kolbe utstyrt med en mekanisk omrører, termometer, kondensator og nitrogeninnløp fylles med 186,6 A 1-liter 3-necked flask equipped with a mechanical stirrer, thermometer, condenser, and nitrogen inlet is filled with 186.6
g (0,03 mol) polydimetylsiloksan-triol (DOW CORNING væske 1248), som hadde blitt strippet fri for flyktige bestanddeler ved å passere det gjennom en strøket-film fordamper. Deretter tilsettes 21,0 g ( 0, 0945 mol) l-isocyanatmetyl-5-isocyanat-1,3,3-trimetyl-cykloheksan (isoforon-diisocyanat, IPDI) sammen med 0,025 g dibutyltinn-dilaurat som katalysator. Blandingen omrøres deretter under nitrogen på et temp-eraturkontrollert vannbad ved 50°C i 5 timer. Ved denne tid hadde NCO innholdet som bestemt ved titrering falt til 1,94% (2,00% teoretisk). g (0.03 mol) of polydimethylsiloxane-triol (DOW CORNING liquid 1248), which had been stripped of volatiles by passing it through a coated-film evaporator. 21.0 g (0.0945 mol) of 1-isocyanatemethyl-5-isocyanate-1,3,3-trimethyl-cyclohexane (isophorone diisocyanate, IPDI) are then added together with 0.025 g of dibutyltin dilaurate as catalyst. The mixture is then stirred under nitrogen on a temperature-controlled water bath at 50°C for 5 hours. At this time, the NCO content as determined by titration had fallen to 1.94% (2.00% theoretical).
Deretter fortynnes 169,4 g polydimetylsiloksan-triisocyanat forpolymer som fremstilt ovenfor, med 10,2 g 2-hydroksyetyl-metakrylat (HEMA) og omrøres under nitrogen ved værelsestemperatur inntil alle NCO-grupper har blitt omsatt som bestemt ved fraværet av isocyanat båndet fra det innfrarøde spektrum. Det resulterende produkt består av >99,9% metakrylat med endestående polysiloksan og mindre mengde av HEMA-endeavsluttet IPDI som vist at noe kjedeforlengelse hadde funnet sted. Dette ble også bekreftet ved gelgjennomtrengningskromatografi. Next, 169.4 g of polydimethylsiloxane-triisocyanate prepolymer as prepared above is diluted with 10.2 g of 2-hydroxyethyl methacrylate (HEMA) and stirred under nitrogen at room temperature until all NCO groups have been reacted as determined by the absence of the isocyanate band from the infrared spectrum. The resulting product consists of >99.9% polysiloxane-terminated methacrylate and a minor amount of HEMA-terminated IPDI indicating that some chain extension had occurred. This was also confirmed by gel permeation chromatography.
Eksempler 2- 17. Examples 2-17.
Fremstilling av polymer prøver. Preparation of polymer samples.
3 0 g hver av polysiloksan makromeren som fremstilt i henhold til eksempel 1 blandes med komonomerer i forholdene som er vist i tabell 1. 0,06 g (0,2%) 1-hydroksycykloheksyl-fenylketon, (UV)-initiator S) tilsettes og hver blanding avgasses grundig og lagres deretter under nitrogen. En porsjon av hver blanding anvendes for fremstilling av 0,1 30 g each of the polysiloxane macromer as prepared according to Example 1 are mixed with comonomers in the conditions shown in Table 1. 0.06 g (0.2%) 1-hydroxycyclohexyl-phenylketone, (UV)-initiator S) is added and each mixture is thoroughly degassed and then stored under nitrogen. A portion of each mixture is used to make 0.1
mm tykke filmer mellom silan-behandlede glassplater, 0,1 mm thick films between silane-treated glass plates, 0.1
mm tykk MYLAR (polyesterfilm fra DuPont) anvendes som et avstandsmiddel og formen holdes sammen med klemmer. Formene utsettes for UV-lys fra en "Black Light Blue" (SYLVANIA) lampe i 3 timer, etter hvilken tid polymeren fjernes fra formen og anvendes for oksygen permeabilitetsmålinger. mm thick MYLAR (polyester film from DuPont) is used as a spacer and the mold is held together with clamps. The molds are exposed to UV light from a "Black Light Blue" (SYLVANIA) lamp for 3 hours, after which time the polymer is removed from the mold and used for oxygen permeability measurements.
På samme måte støpes et 1 mm tykt ark fra hver monomer-makromer blanding og anvendes for bestemmelse av fukteevne. In the same way, a 1 mm thick sheet is cast from each monomer-macromer mixture and used to determine wetting ability.
Ennå en annen part av hver monomer-makromer blanding fylles med en fast-volum sprøyte i sylindriske polypropylen-former med 14 mm diameter og 8 mm høyde og lukkes med et løst passende, konveks polypropylenlokk. Formene innsettes på en rist og bestråles i en nitrogenspylt boks ved anvendelse av lampene som beskrevet ovenfor, først nedenfor kun inntil blandingen er helt dannet (15 minutter) og deretter ovenfra og ned for totalt 3 timer. Deretter åpnes formene og poly- knappen fjernes. Flere knapper kuttes i halvdeler, både parallelt og normalt til den runde overflate og de skjærte overflater poleres for måling av hårdhet. Yet another portion of each monomer-macromer mixture is filled with a fixed-volume syringe into cylindrical polypropylene molds of 14 mm diameter and 8 mm height and closed with a loose-fitting, convex polypropylene cap. The molds are placed on a rack and irradiated in a nitrogen-flushed box using the lamps as described above, first below only until the mixture is fully formed (15 minutes) and then from above downwards for a total of 3 hours. Then the shapes are opened and the poly button is removed. Several buttons are cut in halves, both parallel and normal to the round surface, and the cut surfaces are polished to measure hardness.
Verdier i den følgende tabell viser virkningen av valgte komonomerer på C^-DK, fukteevne og hårdhet. Disse polymerer har Young's modulus verdier på >l(GPa). De følgende eksempler viser virkningen av polysiloksan-makromer-innehold på G^DK og fukteevne. Values in the following table show the effect of selected comonomers on C^-DK, wettability and hardness. These polymers have Young's modulus values of >1(GPa). The following examples show the effect of polysiloxane macromer content on G^DK and wettability.
Eksempler 18- 26. Examples 18-26.
Ved å følge prosedyren som besrkevet i de tidligere eksempler 2-17 blandes makromeren som fremstilt i eksempel 1, med forskjellige mengder av monomerer som vist i tabell 2, og blande-polymeres til 0,1 mm og 1,0 mm tykke filmer. Polymerene teste som beskrevet for oksygenpermeabilitet og fukteevne. Following the procedure described in the previous Examples 2-17, the macromer as prepared in Example 1 is mixed with various amounts of monomers as shown in Table 2, and blend-polymerized into 0.1 mm and 1.0 mm thick films. The polymers test as described for oxygen permeability and wettability.
Eksempler 27- 29. Examples 27-29.
De følgende eksempler viser virkningen ved anvendelse av The following examples show the effect of using
en hydrofil komonomer (dimetylakrylamid). De samme prosedyrer som beskrevet i eksempler 18-26 blir fulgt. a hydrophilic comonomer (dimethylacrylamide). The same procedures as described in Examples 18-26 are followed.
Eksempler 30- 34 Examples 30-34
De følgende eksempler viser virkningen av ytterligere kryssbindingsmidler på G^DK, fukteevne og hårdhet. The following examples show the effect of additional cross-linking agents on G^DK, wettability and hardness.
Ved å følge prosedyren som beskrevet i eksemplene 2-17, blandes makromeren som fremstilt i eksempel 1 med komonomerer i forhold som vist i tabellen. Blandingene ble polymerisert og testet som beskrevet. By following the procedure described in Examples 2-17, the macromer as prepared in Example 1 is mixed with comonomers in proportions as shown in the table. The mixtures were polymerized and tested as described.
Eksempler 35- 38. Examples 35-38.
Prosedyren fra eksempel 1 gjentas, men mengden av isoforon diisocyanat (IPDI) økes fra 0,0945 mol (tilsvarende til et 5% molart overskudd av NCO/OH) til The procedure from example 1 is repeated, but the amount of isophorone diisocyanate (IPDI) is increased from 0.0945 mol (corresponding to a 5% molar excess of NCO/OH) to
0,105 (16,7% molart overskudd av NCO) eks: 35 0,166 (84,4% molart overskudd av NCO) eks: 36 0,243 (170,0% molart overskudd av NC0)eks: 37 0,335 (272,2% molart overskudd av NCO) eks: 38. 0.105 (16.7% molar excess of NCO) ex: 35 0.166 (84.4% molar excess of NCO) ex: 36 0.243 (170.0% molar excess of NC0)ex: 37 0.335 (272.2% molar excess of NCO) ex: 38.
Etter omsetning av det NCO-endestående forpolymer medHEMA for en blanding av 30 deler metakrylat med endestående polysiloksan, 4 deler HEMA, og 1, 5, 10 og 16 deler av reaksjonsproduktet av 2 mol HEMA og 1 mol (IPDI (IPDI-dihema), som bestemt ved gel gjennomtrengningskromatografi. After reacting the NCO-terminated prepolymer with HEMA for a mixture of 30 parts polysiloxane-terminated methacrylate, 4 parts HEMA, and 1, 5, 10, and 16 parts of the reaction product of 2 mol HEMA and 1 mol (IPDI (IPDI-dihema), as determined by gel permeation chromatography.
Blandingene fortynnes med metyl-metakrylat og støpes i form av klare knapper, ark og film med de følgende egenskaper: The mixtures are diluted with methyl methacrylate and cast in the form of clear buttons, sheets and film with the following properties:
Følgende eksempler viser anvendeligheten av polysiloksan-uretan-metakrylatet ved fremstilling av klare og myke oksygen permeable polymerer (med Young's Modulus 1.) for anvendelse som myke kontaktlinser. The following examples show the utility of the polysiloxane-urethane methacrylate in the production of clear and soft oxygen permeable polymers (with Young's Modulus 1.) for use as soft contact lenses.
Eksempler 39. 44. Examples 39. 44.
Polysiloksan makromeren fra eksempel 1 fortynnes med forskjellige komonomerer og 0,1% UV-initiator A og polymeriseres ved innvirkning av UV som beskrevet i eksemplene 2-17. Sammensetninger og egenskaper er vist nedenfor. The polysiloxane macromer from example 1 is diluted with different comonomers and 0.1% UV initiator A and polymerized by exposure to UV as described in examples 2-17. Compositions and properties are shown below.
E ksemplene 45- 48. Examples 45-48.
Polysiloksan makromeren fra eksempel 1 fortynnes med forskjellige komonomerer og 0,2 % UV-initiator A og polymeriseres ved innvirkning av UV som beskrevet i eksemplene 2-17. Det fåes klare polymerer, hvis sammensetninger og egenskaper er vist nednefor: The polysiloxane macromer from example 1 is diluted with various comonomers and 0.2% UV initiator A and polymerized by exposure to UV as described in examples 2-17. Clear polymers are obtained, whose compositions and properties are shown below:
De følgende eksempler viser anvendeligheten av aktiv hydrogen innholdende monomerer andre enn HEMA for fremstilling av polysiloksan forpolymeren. The following examples show the applicability of active hydrogen-containing monomers other than HEMA for the production of the polysiloxane prepolymer.
Eksempler 49- 55. Examples 49-55.
Prosedyren fra eksempel 1 gjentas, men istedet for HEMA anvendes ekvivalente mengder av andre aktiv hydrogeninne-holdende vinylmonomerer for å endeavslutte det NCO-endestående polysiloksan forpolymer. Fullførelsen av slutt-avslutningstrinnet kontrolleres med IR-spektroskopi. På denne måte fremstilles de følgende vinyl-endestående polysiloksaner som klare, viskøse væsker. The procedure from example 1 is repeated, but instead of HEMA, equivalent amounts of other active hydrogen-containing vinyl monomers are used to end the NCO-terminated polysiloxane prepolymer. Completion of the final termination step is checked with IR spectroscopy. In this way, the following vinyl-terminated polysiloxanes are produced as clear, viscous liquids.
De følgende eksempler viser anvendeligheten av polysiloksaner med metakryl, vinyleter og fumarat umettethet ved fremstilling av klare, hårde og G^-permeable polymerer. The following examples show the applicability of polysiloxanes with methacrylic, vinyl ether and fumarate unsaturation in the production of clear, hard and G₂-permeable polymers.
Eksempler 56- 60. Examples 56-60.
De vinyl-endeplasserte polysiloksaner ifølge eksempler 45- The vinyl-terminated polysiloxanes according to Examples 45-
47 fortynnes med monomerer og polymseriseres i form av klare filmer og knapper, ved anvendelse av 0,02% UV-initiator A som initiator. Sammensetningene og deres fysiske egenskaper er oppstillet i den følgende tabell. 47 is diluted with monomers and polymerized in the form of clear films and buttons, using 0.02% UV initiator A as initiator. The compositions and their physical properties are listed in the following table.
Eksempel 61. Example 61.
Ved å følge prosedyren fra eksempel 1, endeavsluttes polydimetylsiloksan-triol (DOW CORNING væske 1248) med isoforon-diisocyanat. Et 10% molart overskudd av metakrylsyre tilsettes sammen med 0,05% kobolta naftenat. CO2utvikles og blandingen holdes ved 50°C i 6 timer etter hvilken tid %-verdien av NCO falt til neste 0. Blandingen fortynnes med 70% metylmetakrylat, 0,1% UV-initiator A tilsettes og polymer ark og filmer fremstilles som beskrevet i eksempel 2. Polymeren er uklar-hvit, har en O2DK på 68 og en oktan/vann kontaktvinkel på 103°. Following the procedure from Example 1, polydimethylsiloxane triol (DOW CORNING liquid 1248) is end-capped with isophorone diisocyanate. A 10% molar excess of methacrylic acid is added together with 0.05% cobalt naphthenate. CO2 is evolved and the mixture is kept at 50°C for 6 hours after which time the % value of NCO has fallen to the next 0. The mixture is diluted with 70% methyl methacrylate, 0.1% UV initiator A is added and polymer sheets and films are prepared as described in Example 2. The polymer is cloudy-white, has an O2DK of 68 and an octane/water contact angle of 103°.
Ekse mpel 62. Example 62.
Ved å følge prosedyren fra eksemplene 1 og 2, fremstilles en polymer ved anvendelse av 2,2,4(2,4,4)-trimetylheksan-1,6-diisocyanat istedet IPDI. Det fåes en polymer med i det vesentlige identiske egenskaper til det fra eksempel 2 . By following the procedure of Examples 1 and 2, a polymer is prepared using 2,2,4(2,4,4)-trimethylhexane-1,6-diisocyanate instead of IPDI. A polymer with essentially identical properties to that from example 2 is obtained.
De følgende eksempler viser anvendeligheten av fluorerte komonomerer ved fremstilling av klare, oksygen permeable polymerer ifølge oppfinnelsen. The following examples show the applicability of fluorinated comonomers in the production of clear, oxygen permeable polymers according to the invention.
Eksempler 63- 68. Examples 63-68.
Ved å følge prosedyren fra eksempler 1 og 2, fremstilles By following the procedure from examples 1 and 2, is prepared
de følgende polymerer og deres oksygen permeabilitet måles. Forkortelsen MA i det fluorerte komonomer betyr metakrylat. the following polymers and their oxygen permeability are measured. The abbreviation MA in the fluorinated comonomer means methacrylate.
Alle prøver er fullstendig klare. All samples are completely clear.
Det følgende eksempel viser at klarheten av polymerer fra eksemplene 63-68 er et uventet resultat da analoge sammensetninger som inneholder intet silikon, gir uforenlige blandinger og svake, opake polymerer: The following example shows that the clarity of polymers from Examples 63-68 is an unexpected result as analogous compositions containing no silicone give incompatible mixtures and weak, opaque polymers:
Eksempel 69. Example 69.
Eksempel 63 gjentas, men siloksan makromeren fra eksempel Example 63 is repeated, but the siloxane macromer from example
1 erstattes med en analog makromer som fåes ved omsetning av 1 mol poly-tetrametylenoksyd-diol (2000 MW) med 2 mol isoforon-diisocyanat, fulgt av ende-avslutning med overskudd HEMA. Det fåes en uforenlig blanding som fase-separerer ved hensetning og underpolymerisasjon. Det dannede poly-merark er opakt, sprøtt og meget svakt. 1 is replaced with an analogous macromer which is obtained by reacting 1 mol of polytetramethylene oxide diol (2000 MW) with 2 mol of isophorone diisocyanate, followed by end termination with excess HEMA. An incompatible mixture is obtained which phase-separates by settling and underpolymerisation. The polymer sheet formed is opaque, brittle and very weak.
De følgende eksempler viser anvendelsen av andre polysiloksaner ved fremstilling av de foreliggende polymerer. The following examples show the use of other polysiloxanes in the production of the present polymers.
Eksempel 70. Example 70.
Ved å følge prosedyren fra eksempel 1, omsettes 21,7 g By following the procedure from example 1, 21.7 g are converted
(0, 025 m) polydimetylsiloksan-diol (DOW CORNING .væske Q4-3557) med 11,7 g (0,0526 m) isoforon-diisocyanat. Etter omrøring under nitrogen i 5 timer ved 50°C faller NCO innholdet til 6,80% (6,90% teoretisk). (0.025 m) of polydimethylsiloxane diol (DOW CORNING .liquid Q4-3557) with 11.7 g (0.0526 m) of isophorone diisocyanate. After stirring under nitrogen for 5 hours at 50°C, the NCO content drops to 6.80% (6.90% theoretical).
Deretter fortynnes 22,3 g av denne polydimetylsiloksan-diisocyanat forpolymer med 5,2 g 2-hydroksyetyl-metakrylat (HEMA) og omrøres ved værelsestemperatur under nitrogen inntil alt NCO er omsatt. Det klare, metakrylat-endeavsluttede polysiloksan lagres kaldt under nitrogen. Det består av 98,2% metakrylat ende-anbragt polysiloksan og 1,8% uomsatt Then 22.3 g of this polydimethylsiloxane-diisocyanate prepolymer is diluted with 5.2 g of 2-hydroxyethyl methacrylate (HEMA) and stirred at room temperature under nitrogen until all the NCO has been converted. The clear, methacrylate-end-capped polysiloxane is stored cold under nitrogen. It consists of 98.2% methacrylate end-capped polysiloxane and 1.8% unreacted
HEMA. HOME.
Deretter fortynnes 20 g av den således fremstilte polysiloksan-dimetylakrylat forpolymer med 20 g metyl-metakrylat. Next, 20 g of the thus produced polysiloxane-dimethylacrylate prepolymer is diluted with 20 g of methyl methacrylate.
0,4 g UV-initiator A innblandes og blandingen avgasses i vakuum. Ved anvendelse av prosedyren som beskrevet i eksempel a, støpes prøver som 0,1 og 1,0 mm tykke filmer og ark, og i form av sylindriske knapper med 14 mm diameter. Den klare polymer har de følgende egenskaper. 0.4 g of UV initiator A is mixed in and the mixture is degassed in a vacuum. Using the procedure as described in example a, samples are cast as 0.1 and 1.0 mm thick films and sheets, and in the form of cylindrical buttons of 14 mm diameter. The clear polymer has the following properties.
Eksempel 71. Example 71.
Ved å følge prosedyren fra eksempel 1, omsettes 28,98 g (0,015 m) av et polydimetylsiloksan (PDMS)-polyetylenoksyd (PEO) blokk kopolymer med strukturen (PEO-PDMS-PEO, som har en ekvivalent vekt på 966 (DOW CORNING væske Q4-3667) med 6,80 g(0,0306 m) isoforon-diisocyanat (PIDI). Etter omrøring under nitrogen i 1 timer ved 50°C, faller NCO- innholdet til 3,87% (3,65% teoretisk) (eller 0,330 ekvivalenter av -NCO). Following the procedure of Example 1, 28.98 g (0.015 m) of a polydimethylsiloxane (PDMS)-polyethylene oxide (PEO) block copolymer having the structure (PEO-PDMS-PEO, having an equivalent weight of 966 (DOW CORNING liquid Q4-3667) with 6.80 g (0.0306 m) of isophorone diisocyanate (PIDI). After stirring under nitrogen for 1 hour at 50°C, the NCO content drops to 3.87% (3.65% theoretical) (or 0.330 equivalents of -NCO).
Deretter blandes 28,72 g av dette NCO-endeavsluttet forpolymer med 6,10 g (0,033 m) t-butylaminoetyl-metakrylat (BAEM) og omrøres ved værelsestemperatur under nitrogen inntil alt NCO er omsatt. Avslutningen av omsetningen kontrolleres med IR-spektroskopi. Den klare, viskøse-metakrylat-endeavsluttede PDMS forpolymer fortynnes med 3 5,2 g metyl-metakrylat og 0,14 g UV-initiator A tilsetes. Etter grundig blanding, støpes massen i form av ark og filmer og polymeriseres ved innvirkning av UV-lys. Next, 28.72 g of this NCO-terminated prepolymer is mixed with 6.10 g (0.033 m) of t-butylaminoethyl methacrylate (BAEM) and stirred at room temperature under nitrogen until all the NCO has been converted. The end of the turnover is checked with IR spectroscopy. The clear, viscous-methacrylate-end-capped PDMS prepolymer is diluted with 35.2 g of methyl methacrylate and 0.14 g of UV initiator A is added. After thorough mixing, the mass is cast in the form of sheets and films and polymerized by exposure to UV light.
Den klare og seige polymer består av 50% metakrylat-endeavsluttet polysiloksan forpolymer og 50% metyl-metakrylat, svelle til likevekt inneholder den 9% vann og har den følg-ende oksygen permeabilitet: 02-DK = 12,3 (9% I^Q); The clear and tough polymer consists of 50% methacrylate-terminated polysiloxane prepolymer and 50% methyl methacrylate, swells to equilibrium it contains 9% water and has the following oxygen permeability: 02-DK = 12.3 (9% I^ Q);
24,3 (tørr). 24.3 (dry).
Eksempel 72. Example 72.
Ved å følge prosedyren fra eksempel 1, omsettes 41,0 g (0,015 m) av en polydimetylsiloksan (PDMS)-ditio med ekvivalent vekt 1367 (DOW CORNING X2-8024) med 6,8 g (0,036 Following the procedure of Example 1, 41.0 g (0.015 m) of a polydimethylsiloxane (PDMS) dithio equivalent weight 1367 (DOW CORNING X2-8024) is reacted with 6.8 g (0.036
m) IPDI, ved anvendelse av 0,02 mg av trietylamin som katalysator. Etter omrøring under nitrogen i 1-1/2 timer ved 24-28°C faller NCO-innholdet til 2,83% (2,74% teoretisk). m) IPDI, using 0.02 mg of triethylamine as catalyst. After stirring under nitrogen for 1-1/2 hours at 24-28°C, the NCO content falls to 2.83% (2.74% theoretical).
Deretter blandes 44,22 g av denne NCO-endeavsluttede forpolymer med 5,96 g av t-butylaminoetyl-metakrylat og omrøres ved værelsestemperatur under nitrogen inntil alt NCO er omsatt. Avslutningen av omsetningen kontrolleres med IR-spektroskopi. Den klare, viskøse metakrylat endeavsluttede PDMS-forpolymer fortynnes med 0,5 g HEMA og 115 g metyl metakrylat og 0,1 g UV-initiator A tilsettes. Etter grundig blanding støpes blandingen i form av ark og filmer og polymeriseres ved inndyrkning av UV-lys. Next, 44.22 g of this NCO-end terminated prepolymer is mixed with 5.96 g of t-butylaminoethyl methacrylate and stirred at room temperature under nitrogen until all the NCO has been converted. The end of the turnover is checked with IR spectroscopy. The clear, viscous methacrylate end-capped PDMS prepolymer is diluted with 0.5 g of HEMA and 115 g of methyl methacrylate and 0.1 g of UV initiator A are added. After thorough mixing, the mixture is cast in the form of sheets and films and polymerized by exposure to UV light.
Den klare polymer som består av 69% metakrylat-endeavsluttet polysiloksan forpolymer, 30,7%MMA og 0,3% HEMA har de følg-ende egenskaper: The clear polymer consisting of 69% methacrylate-terminated polysiloxane prepolymer, 30.7% MMA and 0.3% HEMA has the following properties:
Det følgende eksempel viser syntese av en polymer med et kjedeforlenget polysiloksan. The following example shows the synthesis of a polymer with a chain-extended polysiloxane.
Eksempel 73. Example 73.
Ved å følge prosedyren fra eksempel 1, omsettes 54,66 g (0,02 m) av en polydimetylsiloksan (PDMS)-ditiol med ekvivalent vekt 1367 (DOW CORNING X8024) med 2,10 g (0,01 m) 2,2,4-trimetylheksan-l,6-diisocyanat (TMDI) ved anvendelse av 0,020 g av trietylamin som katalysator. Etter omrøring over natt ved værelsestemperatur (24°C) og under , viser en IR avsøkning at alle isocyanatgrupper er omsatt noe som angir at kjedeforlengelse med 2 molekyler av polydimetylsiloksan-ditiol med 1 molekyl av TMDI har funnet sted. Following the procedure of Example 1, 54.66 g (0.02 m) of a polydimethylsiloxane (PDMS) dithiol of equivalent weight 1367 (DOW CORNING X8024) is reacted with 2.10 g (0.01 m) 2.2 ,4-trimethylhexane-1,6-diisocyanate (TMDI) using 0.020 g of triethylamine as catalyst. After stirring overnight at room temperature (24°C) and below , an IR scan shows that all isocyanate groups have been reacted, indicating that chain extension with 2 molecules of polydimethylsiloxane dithiol with 1 molecule of TMDI has taken place.
56,8 g (0,01 m) av denne kjedeforlengede ditiol er omsatt med 4,53 g (0,0204 m) av IPDI. Reaksjonsblandingen omrøres ved 24°C i 1 1/2 timer ved hvilken tid -NCO innholdet har falt til 1,49% (1,43 % teoretisk). 57,2 g av dette NCO-endeavsluttede forpolymer blandes med 3,75 g t-butyl-amino-etylmetakrylat og omrøres ved 24°C inntil alt NCO er omsatt som kontrollert ved IR-spektroskopi. 56.8 g (0.01 m) of this chain-extended dithiol is reacted with 4.53 g (0.0204 m) of IPDI. The reaction mixture is stirred at 24°C for 1 1/2 hours, by which time the -NCO content has fallen to 1.49% (1.43% theoretical). 57.2 g of this NCO-terminated prepolymer is mixed with 3.75 g of t-butyl-amino-ethyl methacrylate and stirred at 24°C until all the NCO has been converted as checked by IR spectroscopy.
15 g av det metakrylat-endeavsluttede PDMS forpolymer blandes med 35 g metyl-metakrylat og 0,05 g UV-initiator A. Blandingen støpes i form av ark og filmer eller knapper og polymeriseres ved innvirkning av UV-lys som beskrevet i eksempel 2. Den lett uklare polymer har de følgende egenskaper: 15 g of the methacrylate-terminated PDMS prepolymer is mixed with 35 g of methyl methacrylate and 0.05 g of UV initiator A. The mixture is cast in the form of sheets and films or buttons and polymerized by exposure to UV light as described in example 2. The slightly cloudy polymer has the following properties:
De følgende eksempler viser overlegenheten av polymerer som inneholder uretangrupper i forhold til polymerer som inneholder ingen uretangrupper. The following examples demonstrate the superiority of polymers containing urethane groups over polymers containing no urethane groups.
Ekse mpler 74- 76. Examples 74-76.
Po.!ydimetylsiloksan-me takrylater som bærer metakrylat-grupper vedhengende til hovedkjeden og bundet til den ved karbinol-ester bindinger og som er tilgjengelig fra PETRAPCH Chem.. Co, under koden: Polydimethylsiloxane methacrylates bearing methacrylate groups attached to the main chain and bound to it by carbinol ester linkages and which are available from PETRAPCH Chem.. Co, under the code:
fortynnes til 30% med 4% HEMA og 66% cykloheksyl-metakrylat. Til hver 0,1% UV-initiator A tilsettes og blandingene polymeriseres ved innvirkning av UV i form av 0,1 mm og 1,0 mm tykke filmer og ark. Resultatene er vist i den følgende tabell. dilute to 30% with 4% HEMA and 66% cyclohexyl methacrylate. To each 0.1% UV initiator A is added and the mixtures are polymerized by exposure to UV in the form of 0.1 mm and 1.0 mm thick films and sheets. The results are shown in the following table.
Metakrylatestrer fremstilt ved forestering av polydimetylsiloksan-triol (1248) med metakryloyl-klorid og som derfor er lik polysiloksan-metakrylatet ifølge eksempel 1 med unn-tak av fraværet av uretangrupper, gir likeledes opake og svake polymerer når formulert og polymerisert slik som beskrevet ovenfor (eks. 76). Methacrylate esters prepared by esterification of polydimethylsiloxane triol (1248) with methacryloyl chloride and which are therefore similar to the polysiloxane methacrylate according to example 1 with the exception of the absence of urethane groups, likewise give opaque and weak polymers when formulated and polymerized as described above ( e.g. 76).
Det følgende eksempel viser anvendeligheten såvel som overlegenheten av hårde kontaktlinser fremstilt fra polymerene ifølge oppfinnelsen, over tidligere kjente materialer. The following example shows the applicability as well as the superiority of hard contact lenses made from the polymers according to the invention, over previously known materials.
E ksempel. Example.
Runde polymerknapper fra eksempler 30 og 33, støpt på en måte som beskrevet i eksempel 2, med 15 mm diameter og 8 Round polymer buttons from Examples 30 and 33, molded in a manner as described in Example 2, of 15 mm diameter and 8
mm høyde, tilvirket til kontaktlinse former ved dreiing og polering ved anvendelse av konvensjonell teknikk ved hård kontaktlinse-fremstilling. Egnethet for maskinbear-beidelse, overflateglans, hårdhet, ripemotstandsdyktighet og målstabilitet og klarhet av alle prøver er utmerket og ingen forandring i grunnkurven ved hydratisering ble iakt-tatt . mm height, made into contact lens shapes by turning and polishing using conventional techniques in hard contact lens manufacturing. Suitability for machining, surface gloss, hardness, scratch resistance and target stability and clarity of all samples are excellent and no change in the base curve upon hydration was observed.
En polymerknapp fra eksempel 30 ble maskinbearbeidet til A polymer button from example 30 was machined to
en form for å passe elektroden til et oksygen permeabilitets-apparat. C^-permeabilitet måles og sammenlignet med tidligere kjente materialer som også har god målstabilitet og er tilbudt som oksygen permeable, hård kontaktlinse-materiale : a form to fit the electrode of an oxygen permeability apparatus. C^-permeability is measured and compared with previously known materials which also have good target stability and are offered as oxygen permeable, hard contact lens material:
Ingen av de andre syntetiske produkter for fremstilling av Si-inneholdende kontaktlinser gir materialer med så høy oksygenpermeabilitet som kan oppnås med polymerer ifølge oppfinnelsen, mens det samtidig opprettholdet den nødven-dige hårdhet for maskinbearbeiding og polering. None of the other synthetic products for the production of Si-containing contact lenses provide materials with such high oxygen permeability as can be achieved with polymers according to the invention, while at the same time maintaining the necessary hardness for machining and polishing.
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US06/433,743 US4486577A (en) | 1982-10-12 | 1982-10-12 | Strong, silicone containing polymers with high oxygen permeability |
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-
1983
- 1983-08-23 ZA ZA836219A patent/ZA836219B/en unknown
- 1983-10-06 AT AT83810461T patent/ATE21402T1/en not_active IP Right Cessation
- 1983-10-06 DE DE8383810461T patent/DE3365325D1/en not_active Expired
- 1983-10-06 EP EP83810461A patent/EP0109355B1/en not_active Expired
- 1983-10-07 CA CA000438619A patent/CA1258935A/en not_active Expired
- 1983-10-10 IN IN698/DEL/83A patent/IN161231B/en unknown
- 1983-10-10 MX MX199069A patent/MX174438B/en unknown
- 1983-10-10 GR GR72651A patent/GR79680B/el unknown
- 1983-10-10 FI FI833675A patent/FI72736C/en not_active IP Right Cessation
- 1983-10-10 IL IL69942A patent/IL69942A/en not_active IP Right Cessation
- 1983-10-11 NZ NZ205919A patent/NZ205919A/en unknown
- 1983-10-11 DD DD83255579A patent/DD218374A5/en not_active IP Right Cessation
- 1983-10-11 DK DK467583A patent/DK165751C/en not_active IP Right Cessation
- 1983-10-11 NO NO833700A patent/NO162244C/en unknown
- 1983-10-11 AU AU20051/83A patent/AU575026B2/en not_active Ceased
- 1983-10-11 IE IE2390/83A patent/IE56028B1/en not_active IP Right Cessation
- 1983-10-11 PH PH29681A patent/PH19176A/en unknown
- 1983-10-11 PT PT77480A patent/PT77480B/en not_active IP Right Cessation
- 1983-10-11 ES ES526376A patent/ES526376A0/en active Granted
- 1983-10-11 HU HU833513A patent/HU199520B/en not_active IP Right Cessation
- 1983-10-12 CS CS837500A patent/CS242886B2/en unknown
- 1983-10-12 KR KR1019830004817A patent/KR910008282B1/en not_active IP Right Cessation
- 1983-10-12 JP JP58190617A patent/JPH0681786B2/en not_active Expired - Lifetime
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1993
- 1993-08-18 JP JP5225261A patent/JPH0731313B2/en not_active Expired - Lifetime
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